Methyl substituted oxobicyclo-4,4,0-decane derivatives, process for preparing same and organoleptic uses thereof

ABSTRACT

Described are compounds having the generic structure: ##STR1## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; wherein X represents the moieties: ##STR2## wherein R 1 , R 2 , R 3  and R 4  represent hydrogen or methyl with the proviso that (i) at least three of R 1 , R 2 , R 3  and R 4  represent hydrogen and (ii) when the dashed line is a carbon-carbon single bond and X is: ##STR3## then one of R 1 , R 2 , R 3  or R 4  is methyl and the other represents hydrogen; wherein R 5  represents hydrogen, MgX, MgR 7 , CdR 7 , ZnR 7 , Na, K or Li; wherein X represents Chloro, Bromo or Iodo; wherein R 6  represents hydrogren or methyl; and wherein R 7  represents lower alkyl; and uses thereof for their organoleptic properties in augmenting or enhancing or enhancing the aromas or tastes of perfumes, perfumed articles, foodstuffs, chewing gums, smoking tobaccos, toothpastes, medicinal products, chewing tobacco and smoking tobacco articles, as well as processes for preparing same.

This is a divisional of application Ser. No. 182,451, filed Aug. 29,1980, now U.S. Pat. No. 4,320,772.

BACKGROUND OF THE INVENTION

The instant invention covers compounds having the generic structure:##STR4## wherein the dashed line represents a carbon-carbon single bondor a carbon-carbon double bond; wherein X represents the moieties:##STR5## wherein R₁, R₂, R₃ and R₄ represents hydrogen or methyl withthe provisos that (i) at least three of R₁, R₂, R₃ and R₄ representhydrogen and (ii) when the dashed line is a carbon-carbon single bondand X is: ##STR6## then one of R₁, R₂, R₃ or R₄ is methyl and the otherrepresents hydrogen; wherein R₅ represents hydrogen, MgX, MgR₇, CdR₇,ZnR₇, Na, K or Li; wherein X represents Chloro, Bromo or Iodo; whereinR₆ represents hydrogen or methyl; and wherein R₇ represents lower alkyl;as well as uses of the above compounds, with the exception of theorganometallic compounds of the genus, for augmenting or enhancing thearomas and/or taste of consumable materials.

Materials which can provide minty, camphoraceous, dry woody, sweet,fruity, woody patchouli, green, herbaceous, basil-like, citrus-like,bergamot-like, lime-like, grapefruit-like, peppery, precious-woody,vertiver-like, fresh, musky, lavender thyme, rosemary, sweaty, rooty andearthy aromas with floral, citrus, lavender and amber top-notes andbackgrounds are known in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute desired nuancesto perfumery compositions are high in cost, vary in quality from onebatch to another and/or are generally subject to the ususal variationsof natural products.

By the same token, materials which can provide oriental, insence-like,peppery, blueberry-like, eucalyptol-like, minty, camphoraceous, floral,musk-like, rose-like, black pepper, spicey, patchouli, cooling,sandalwood-like, woody and walnut-like aromas with oriental, blackpepper, peppery, minty, eucalyptol-like, camphoraceous, floral, roseyand patchouli-like tastes are well known in the art of flavoring forfoodstuffs, toothpastes, chewing gums and medicinal products. Many ofthe natural materials which provide such flavor nuances and contributedesired nuances to flavor and compositions are high in cost, vary inquality from one batch to another and/or are generally subject to theusual variations of natural products.

Sweet, fruity, berry-like, cooling, woody and floral aroma and tastenuances are known in the art of the production of smoking tobaccos andsmoking tobacco articles. Many of the natural materials which providesuch aroma and taste nuances to smoking tobacco compositions are high incost, vary in quality from one batch to another and/or are generallysubject to the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the essential flavor and/orfragrance notes provided by natural essential oils or compositionsthereof. Unfortunately, many of these synthetic materials either havethe desired nuances only to a relatively small degree or else contributeundesirable or unwanted odor to the consumable compositions. The searchfor materials which can provide more refined patchouli-like aromas, forexample, have been difficult and relatively costly in the areas of bothnatural products and synthetic products.

Artificial flavoring agents for foodstuffs have received increasingattention in recent years. For many years such food flavoring agentshave been preferred over natural flavoring agents at least in part dueto their diminished cost and their reproducible flavor qualities. Forexample, natural food flavoring agents such as extracts, concentratesand the like are often subject to wide variations due to changes inquality, type and treatment of the raw materials. Such variations can bereflected in the end products and result in unfavorable flavorcharacteristics in said end product. Additionally, the presence of thenatural product in the ultimate food may be undesirable because ofincreased tendency to spoil. This is particularly troublesome in foodand food uses where such products as dips, soups, chips, sausages,gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that theartificial flavor to be achieved be as natural as possible. Thisgenerally proves to be a difficult task since the mechanism for flavordevelopment in many foods, medicinal products, chewing gums andtoothpastes is not completely known. This is noticable in productshaving licorice, citrusy and vegetable flavor characteristicsparticularly.

Even more desirable are products that can serve to substitute fordifficult-to-obtain natural perfumery oils and at the same timesubstitute for natural flavoring ingredients in foodstuffs, chewinggums, medicinal products, toothpastes, and smoking tobaccos.

Oxobicyclo compounds are known in the prior art. Thus, Nagakura, et al,Bull, Chem. Soc. Japan Vol. 48(10), 2995-6 (October 1975) discloses thecompound defined according to the generic structure: ##STR7## producedby the reaction: ##STR8## wherein one of R₁ ', R₂ ', R₃ ' or R₄ ' ismethyl and the others represent hydrogen. In addition, Conia andRouessac, Bull. Soc. Chem. France 1953 (page 1925 et seq.) disclosesprocesses for producing oxobicyclo compounds according to the followingreaction steps: ##STR9##

The use of oxotricyclic derivatives in perfumery is disclosed in U.S.Pat. No. 3,996,169, issued on Dec. 7, 1976. Thus, in U.S. Pat. No.3,996,169, a genus defined according to the structure: ##STR10## isdisclosed, wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ isselected from the group consisting of hydrogen and methyl; and whereinthe dashed line may be a carbon-carbon single bond or a carbon-carbondouble bond. Members of this genus are indicated to be capable ofaltering, modifying, enhancing or emparting an aroma of or to consumablematerials including colognes, perfumes and perfumed articles and such anaroma is of a patchouli type.

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1 discloses theuse in perfume compositions and foodstuff flavors of "decalinol","decalone", "fenchone", and "fenchyl alcohol", thusly:

"(i) 1385: FENCHONE

laevo-Fenchone. (dextro- is known but less common as a fragrancematerial).

1,3,3-Trimethyl-2-norbornanone. 1,3,3-Trimethyl bicyclo-1,2,2-heptone-2.##STR11## Warm-camphoraceous, powerful and diffusive, basically sweetodor. Warm, somewhat burning and bitter taste with a medicinal note.

This ketone finds some use as a masking odor in industrial fragrances.It is also used in the reconstruction of Fennel oil and a few otheressential oils.

In spite of its rather unpleasant taste, it is used in various Berrycomplex flavors, in Spice complexes and in certain types of Liquerflavoring.

The concentration used is about 0.1 to 5 ppm in the finished product.

(ii) 1387: FENCHYL ALCOHOL

1,3,3-Trimethyl-2-norbornanol. 1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2.2-Fenchanol. Fenchol. ##STR12## The racemic alpha-Fenchol has a somewhatlower melting point, and the beta-Fenchols are all liquid at roomtemperature.

Fenchol made by reduction of Fenchone from Cedarleaf oil is usually amixture of several isomers, including the crystalline alpha-isomers. Thebeta-isomer forms a crystalline Hydrate which may be solid at roomtemperature.

Almost insoluble in water, soluble in alcohol, miscible with oils.Powerful and diffusive, Camphor-like, but sweeter and more Citrus-likealmost Lime-like odor with more or less of an earthy-dry character,according to the composition and isomer-ratio.

The taste is somewhat bitter-Lime-like, camphoraceous and slightlywoody-musty.

This interesting alcohol (or mixed alcohols) finds use in perfumecompositions ranging from woody or herbaceous to Citrus-Lime and evencertain floral types. It produces power and `lift` to floral fragrances,and solid background to Lime and other Citrus bases, having theadvantage over the Terpenes in being very stable in soap.

Fenchyl alcohol is also used in flavor compositions such as Strawberryand other berries, Lime and Spice, etc.

The concentration is normally low, e.g. 0.2 up to 5 ppm in the finishedproduct.

(iii) 824: TRANS-DECAHYDRO-BETA-NAPHTHOL

trans-beta-Decanol. (sometimes called "Decalinol".)Bicyclo-4,4,0-Decanol ##STR13## Colorless viscous liquid, solidifying inthe cold to an opaque mass. The presence of variable amounts of thecis-isomer is mainly responsible for the variations in physicalappearance of this material.

Mild, sweet, slightly camphoroaceous-woody, also warm and mildly spicyodor of fair tenacity. The odor has been compared to that ofDihydrocarveol, but such description does not help many perfumers.

Practically insoluble in water, soluble in alcohol and oils.

This alcohol has been used, and is still used on a mosdest scale, inperfume compositions, mostly in connection with woody and camphoraceousfragrance types, including the Ionones, Cyclohexylderivatives, etc.Several of its esters (see following monographs) have been moresuccessful as perfume materials).

However, since the Ambregis- and Sandalwood-notes, which are representedto a certain degree in the esters, can be obtained with much superiorbeauty by way of modern perfume chemicals, there is reason to believethat the Decahydronaphthyl series will eventually becomre obsolete.

Prod.: by catalytic hydrogenation of beta-Naphthol. The reaction yieldsa mixture of cis- and trans-isomers, but the perfumers generally preferthe trans-isomer or a material primarily consisting of that isomer.

(iv) 830: BETA-DECALONE

Decahydro naphthalone

The commercial products consist of a mixture of cis- and trans-isomers.##STR14## Viscous colorless liquid, solidifying in the cold. Practicallyinsoluble in water, soluble in alcohol and oils.

The cis-isomer is liquid and boils at 247° C.

The trans-isomer is solid below 6° C. and boils at 241° C.

Semi-dry, tenacious odor resembling part of the Ambregris-picture, alsowoody, remotely reminiscent of Sandalwood. Odor variations are observedin materials from different sources of supply.

This ketone has found a little use in perfume compositions, includingsoap perfumes, where it can introduce pleasant background notes insupport of Musk Ambrette, Labdanum, Methylionones, etc.

Recent development in Ambregris chemicals has brought much superiormaterials in the hands of the perfumer, and it is very likely that thetitle material, and many of its relatives, will become obsolete withinthe next decade or so.

Prod.: by oxidation of beta-Decalol with Chromic acid mixture."

U.S. Pat. No. 3,932,515 discloses the use of the compound having thestructure: ##STR15## in perfumery and specifically indicates that suchcompound has a woody aroma of high tenacity. U.S. Pat. No. 3,932,516discloses the compound having the structure: ##STR16## and indicatesthat this compound is useful in perfumery due to its woody character.

None of the references cited above, or for that matter any otherreferences discloses compounds which have a close structuralrelationship to the genus of compounds of the instanct invention. In anyevent, the organoleptic properties of the compounds of the referencesare different in kind from those of the compounds of the instantinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR17##

FIG. 2 is the mass spectrum for the product of Example I having thestructure: ##STR18##

FIG. 3 represents the NMR spectrum for the product of Example I havingthe structure: ##STR19##

FIG. 4 represents the infrared spectrum for the product of Example Ihaving the structure: ##STR20##

FIG. 5 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR21##

FIG. 6 is the mass spectrum for the product of Example II having thestructure: ##STR22##

FIG. 7 is the NMR spectrum for the product of Example II having thestructure: ##STR23##

FIG. 8 is the infrared spectrum for the product of Example II having thestructure: ##STR24##

FIG. 9A represents the GLC profile for the major product of Example III.

FIG. 9 is the GLC profile for the reaction product of Example IIIcontaining the compounds having the structures: ##STR25## (fraction 2 ofone-plate distillation, "Rushover")

FIG. 10 is the mass spectrum for the product of Example III having thestructures: ##STR26##

FIG. 11 is the NMR spectrum for the product of Example III having thestructures: ##STR27##

FIG. 12 is the infrared spectrum for the product of Example III havingthe structures: ##STR28##

FIG. 13A is the GLC profile for the reaction mixture of Example IV(fraction 3, "cis-isomer") containing the compounds having thestructures: ##STR29##

FIG. 13B is the GLC profile for the reaction mixture of Example IVspiked with reactant and thus containing the compounds having thestructures: ##STR30##

FIG. 14 is the mass spectrum for the reaction product of Example IV,fraction 3, containing the compounds having the structures: ##STR31##

FIG. 15 is the NMR spectrum for the reaction product of Example IV,containing the compounds having the structures: ##STR32##

FIG. 16 is the infrared spectrum for the reaction product of Example IV,fraction 3, containing the compounds having the structures: ##STR33##

FIG. 17 is the GLC profile for the reaction product of Example Vcontaining the compounds having the structures: ##STR34##

FIG. 18 is the mass spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR35##

FIG. 19 is the NMR spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR36##

FIG. 20 is the infrared spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR37##

FIG. 21 is the GLC profile for the reaction product of Example VI(A),fraction 7, containing the compounds having the structures: ##STR38##

FIG. 22 is the mass spectrum for the reaction product of Example VI(A),fraction 7, containing the compounds having the structures: ##STR39##

FIG. 23 is the NMR spectrum for the reaction product of Example VI(A)containing the compounds having the structures: ##STR40##

FIG. 24 is the infrared spectrum for the reaction product of ExampleVI(A) containing the compounds having the structures: ##STR41##

FIG. 25 is the GLC profile for the reaction product of Example VI(B)(bulked fractions 2-7) containing the compounds having the structures:##STR42##

FIG. 26A is the GLC profile for the crude product of the reaction ofExample VII(A) containing the compound having the structure: ##STR43##

FIG. 26B is the GLC profile for bulked fractions 1-3 of the distillationproduct of the reaction product of Example VII(A) containing thecompound having the structure: ##STR44##

FIG. 27 is the mass spectrum for the reaction product of Example VII(A),bulked fractions 1-3, containing the compound having the structure:##STR45##

FIG. 28 is the NMR spectrum for the reaction product of Example VII(A),bulked fractions 1-3, containing the compound having the structure:##STR46##

FIG. 29 is the infrared spectrum for the reaction product of ExampleVII(A), bulked fractions 1-3, containing the compound having thestructure: ##STR47##

FIG. 30 is the GLC profile for the reaction product, after 1.5 hours ofExample VII(B) containing the compound having the structure: ##STR48##

FIG. 31 is the GLC profile for the reaction products, of Example VII(B),spiked with reactant, containing the compounds having the structures:##STR49##

FIG. 32 is the GLC profile for the reaction product of Example VIIIcontaining the compounds having the structures: ##STR50##

FIG. 33 is the mass spectrum for the reaction product of Example VIIIcontaining the compounds having the structures: ##STR51##

FIG. 34 is the NMR spectrum for the reaction product of Example VIII,fraction 3, containing the compounds having the structures: ##STR52##

FIG. 35 is the infrared spectrum for fraction 3 of the distillationproduct of the reaction product of Example VIII containing the compoundshaving the structures: ##STR53##

FIG. 36 is the GLC profile for the reaction product of Example IXcontaining the compounds having the structures: ##STR54##

FIG. 37 is the mass spectrum for the reaction product of Example IXcontaining the compounds having the structures: ##STR55##

FIG. 38 is the NMR spectrum for the distillation product, fraction 4, ofthe reaction product of Example IX containing the compounds having thestructures: ##STR56##

FIG. 39 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example IX containing the compoundshaving the structures: ##STR57##

FIG. 40 is the GLC profile for the reaction product of Example X,containing the compound having the structure: ##STR58##

FIG. 41 is the mass spectrum for the reaction product of Example X,containing the compound having the structure: ##STR59##

FIG. 42 is the NMR spectrum for fraction 1 of the distillation productof the reaction product of Example X, containing the compound having thestructure: ##STR60##

FIG. 43 is the infrared spectrum for fraction 1 of the distillationproduct of the reaction product of Example X, containing the compoundhaving the structure: ##STR61##

FIG. 44 is the GLC profile (fraction 3) for the reaction product ofExample XI containing the compounds having the structures: ##STR62##

FIG. 45 is the mass spectrum for the reaction product of Example XI,containing the compounds having the structures: ##STR63##

FIG. 46 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example XI containing the compounds havingthe structures: ##STR64##

FIG. 47 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XI containing the compoundshaving the structures: ##STR65##

FIG. 48 is the GLC profile for the crude reaction product after initialworkup of Example XII containing the compound having the structure:##STR66##

FIG. 49 is the mass spectrum for the reaction product of Example XIIcontaining the compound having the structure: ##STR67##

FIG. 50 is the NMR spectrum for fraction 6 of the distillation productof the reaction product of Example XII containing the compound havingthe structure: ##STR68##

FIG. 51 is the infrared spectrum for fraction 6 of the distillationproduct of the reaction product of Example XII containing the compoundhaving the structure: ##STR69##

FIG. 52 is the GLC profile for fraction 2 of the one-plate distillationproduct of the reaction product of Example XIII containing the compoundshaving the structures: ##STR70##

FIG. 53 is the mass spectrum for the reaction product of Example XIIIcontaining the compounds having the structures: ##STR71##

FIG. 54 is the NMR spectrum for fraction 6 of the distillation productof the reaction product of Example XIII containing the compounds havingthe structures: ##STR72##

FIG. 55 is the infrared spectrum for fraction 6 of the distillationproduct of the reaction product of Example XIII containing the compoundshaving the structures: ##STR73##

FIG. 56 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example XIV containing the compounds having thestructures: ##STR74##

FIG. 57 is the mass spectrum for the reaction product of Example XIVcontaining the compounds having the structures: ##STR75##

FIG. 58 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example XIV containing the compounds havingthe structures: ##STR76##

FIG. 59 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XIV containing the compoundshaving the structures: ##STR77##

FIG. 60 is the GLC profile for the reaction product of Example XVcontaining the compound having the structure: ##STR78##

FIG. 61 is the mass spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR79##

FIG. 62 is the NMR spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR80##

FIG. 63 is the infrared spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR81##

FIG. 64 is the GLC profile of the reaction product (after 8 hoursreflux) for Example XVI containing the compounds having the structures:##STR82##

FIG. 65 is the mass spectrum for the reaction product of Example XVIcontaining the compounds having the structures: ##STR83##

FIG. 66 is the NMR spectrum of fraction 4 of the distillation product ofthe reaction product of Example XVI containing the compounds having thestructures: ##STR84##

FIG. 67 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XVI containing the compoundshaving the structures: ##STR85##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having oriental, incense-like, peppery,blueberry-like eucalyptol-like, minty, camphoraceous, floral, musk-like,rose-like, black pepper, spicey, patchouli, cooling, sandalwood-like,woody and walnut-like aromas with oriental, black pepper-like, peppery,minty, eucalyptol-like, camphoraceous, floral, rosey and patchouli-liketastes; as well as novel smoking tobacco and smoking tobacco flavoringcompositions having sweet, fruity, berry-like, cooling, woody and floralaromas prior to smoking and on smoking in both the mainstream and thesidestream; as well as novel perfume compositions, colognes and perfumedarticles (e.g. solid or liquid anionic, cationic, nonionic andzwitterionic detergents, fabric softener compositions, cosmetic powdersand prior-added faric softener articles) having intense and pleasantminty, camphoraceous, dry woody, sweet fruity, patchouli, woodypatchouli, green, herbaceous, basil-like, citrus-like, bergamot-like,lime-like, grapefruit-like, peppery, precious woody, vetiver, fresh,musky, lavender, thyme, rosemary, sweaty, rooty and earthy aromas withfloral, citrus, lavender, and amber-like top-notes and undertones may beprovided by the utilization of one or more methyl substitutedoxobicyclo-4,4,0-decane derivatives of our invention having the genericstructure: ##STR86## wherein X is a moiety which is either: ##STR87##wherein the dashed line represents a carbon-carbon single bond or acarbon-carbon double bond; wherein R₁, R₂, R₃ and R₄ represent hydrogenor methyl with the provisos (i) that at least three of R₁, R₂, R₃ and R₄represent hydrogen and the other of R₁, R₂, R₃ and R₄ is methyl and (ii)that when the dashed line is a carbon-carbon single bond and X is themoiety: ##STR88## then one of R₁, R₂, R₃ or R₄ is methyl and the otherof R₁, R₂, R₃ or R₄ is hydrogen; wherein R₅ represents hydrogen and R₆represents hydrogen or methyl in foodstuffs, chewing gums, toothpastes,medicinal products, perfume compositions, perfumed articles, colognesand smoking tobaccos as well as smoking tobacco substitutes.

Unless otherwise specified, representations herein of organic structuresare intended to indicate a "cis" isomer a "trans" isomer, or a mixtureof "cis" and "trans" isomers with respect to the plane of thecyclohexane or the cyclohexane ring. Thus, the generic structure:##STR89## may either be a "cis" isomer, for example, having thestructure: ##STR90## or a "trans" isomer having the structure: ##STR91##

Furthermore, the "trans" structure: ##STR92## with respect to the methylmoiety at the "-9,10-" position may further be specified, for example,by the structure: ##STR93## wherein X is >CHOH.

The methyl substituted oxobicyclo-4,4,0-decane derivatives of ourinvention may be prepared by first reacting2,6,6-trimethylcyclohex-2-enone with a substituted butadiene such asbutadiene, isoprene or piperylene according to the reaction: ##STR94##The ratio of diene:ketone may be in the range of from about 1:1 (moleratio) up to about 10:1 with a mole ratio of diene:ketone preferablybeing about 1.5:1. The reaction may be carried out in the presence of aLewis acid catalyst such as aluminum thrichloride, zinc chloride,titanium tetrachloride, BF₃.etherate, ethyl aluminum dichloride, diethylaluminum chloride, and other Lewis acid catalysts. Reaction may becarried out in the presence of or in the absence of a solvent. Whenusing a solvent, solvents such as toluene, xylene and chlorinatedsolvents may be used which are inert to the reactants.

The reaction may be carried out at the temperatures of between 31 15° C.and 100° C.; preferably at -10° C. up to about 50° C. The reaction maybe carried out at atmospheric pressure, super atmospheric pressures andsubatmospheric pressures. Most conveniently, economically and preferablythe reaction is carried out at atmospheric pressure.

The resulting ketone may be used as is for its organoleptic properties,in which case, the resulting ketone is purified as by standardextraction and fractional distillation processes. The isomers resultingmay be commercially separated as by means of high pressure liquidchrometography.

The resulting ketone may, however, be further reacted either (i) bymeans of a reduction reaction to form a saturated ketone according tothe reaction: ##STR95## or (ii) by reduction of the ketone moiety toform an alcohol by means of the reaction: ##STR96## or (iii) by means ofreaction with an organometallic compound such as a Grignard reagentfollowed by subsequent hydrolysis whereby the 1-methyl-1-hydroxyderivative is formed according to the reaction scheme: ##STR97## whereinM is either of MgX, Na, K, Li, Cd, Mg or Zn; wherein X is chloro, bromoor iodo; wherein R₇ is lower alkyl; wherein when M is Cd, Mg or Zn, n=1and when M is MgX, Na, K or Li, n=0. The resulting unsaturated alcoholmay further be reduced as by hydrogenation, for example, according tothe reaction: ##STR98##

When a hydrogenation reaction is carried out, e.g.: ##STR99## ahydrogenation catalyst is used, for example, a palladium catalyst or apalladium-on-carbon catalyst whereby a saturated ketone is formed. Thehydrogenation is preferably carried out at temperatures in the range offrom about 20° C. up to about 100° C. at pressures of between about 30psig and about 300 psig; preferably at pressures of between 40 psig and60 psig. At the end of the hydrogenation, the resulting ketone may beused for its organoleptic properties in which case the resulting ketoneis purified by means of standard extraction procedures and standardfractional distillation procedures. In the event that two or moreisomers are formed as a result of the reaction, the resulting isomersmay be separated as by means of fractional distillation or even by meansof high pressure liquid chomotography.

When the ketone moiety is reduced to the alcohol as by means of thereaction: ##STR100## this reaction takes place using a reducing agentsuch as lithium aluminum hydride, sodium boro hydride, lithiumborohydride. Al(isobutyl)₂ H or "Vitride®" which is NaAlH₂ (OCH₂ CH₂OCH₃)₂. However, the ketone moiety may be reduced to the alcohol moietyby means of high pressure and high temperature hydrogenation, e.g.carrying out a hydrogenation at about 90°-150° C. at pressure of between50 and 5,000 psig. The higher pressure and higher temperature range willgive rise to shorter reaction time.

The resulting ketone may be used as is or may be further reacted with anorganometallic compound which is subsequently hydrolyzed. Thus, in theresulting ketone is to be used "as is" for its organoleptic properties,said ketone will be further "workup" as by means of standard extractionprocedures and/or fractional distillation procedures. In the event thatpure isomers are desired and indeed pure stereoisomers are desired, highpressure liquid chromotographic techniques may be used as well asstandard stereoisomer-separation techniques using pure stereoisomerswhich will react with a functional group followed by decomposition afterfractional crystallization, for example.

When the resulting ketone is reacted with an organometallic compound toform a second organometallic compound which is subsequently hydrolizedaccording to the reaction procedure: ##STR101##

In the reaction of the oxabicyclic ketone with the organometalliccompound having the structure:

    CH.sub.3 --M(R.sub.7).sub.n

it is preferred that the compound having the structure:

    CH.sub.3 --M(R.sub.7).sub.n

be reacted in an appropriate solvent such as benzene,benzene/tetrahydrofuran, tetrahydrofuran or diethyl ether. It is alsopreferred that the mole ratio of organometallic compound having thestructure:

    CH.sub.3 --M(R.sub.7).sub.n : Ketone

be about 1:1. It is further preferred that the reaction temperature befrom about -5° C. up to about 40° C. with the most preferred temperaturebeing 20° C.-30° C.

The hydrolysis of the organometallic compound to form the resultingalcohol is carried out using a mineral acid such as dilute aqueoushydrochloric acid, sulfuric acid or phosphoric acid or other protonicacids such as paratoluenesulfonic acid. The hydrolysis preferably takesplace at 0°-20° C. At the end of this reaction, the reaction product isisolated by means of standard isolation techniques such as fractionaldistillation and, if desired, preparative GLC or high pressure GLC forisolation of the end product.

An alternative method for preparing unsaturated alcohols of ourinvention is to react the ketones resulting from the Diels-Alderreaction with isopropyl magnisium halide. In view of the stericallyhindered position of the ketone (as a result of the methyl groups"alpha" to the ketone moity), an oxygrignard is formed from the ketonewithout alkylation at the ketone moity. The resulting oxygrignard maythen be hydrolized using standard hydrolisis conditions as set forthabove to yield the resulting alcohol. The reaction illustrating thisprocedure is set forth as follows: ##STR102##

Specific examples of compounds produced according to the foregoingprocess are set forth in Table I below:

                                      TABLE I                                     __________________________________________________________________________                                         Smoking                                  Structure of                                                                            Name of  Perfumery                                                                              Flavor   Tobacco                                  Compound  Compound Evaluation                                                                             Evaluation                                                                             Evaluation                               __________________________________________________________________________     ##STR103##                                                                             3,4,4A,5,8,8A- Hexahydro-2,2, 8A-trimethyl- 1 (2H)-naphtha-                   lenone (major- ity: "cis" isomer).                                                     Minty, campho- raceous, dry woody with floral citrus                          background.                                                                            An oriental incense, peppery aroma with an an                                 oriental and peppery flavor characteristic at                                 1 ppm.                                            Produced according                                                            to Example I                                                                   ##STR104##                                                                             Octahydro-2,2, 8A-trimethyl- 1 (2H)-naphtha- lenone.                                   A sweet, frui- ty, minty camphoraceous aroma with a                           woody patchouli undertone flavor charac- teristic.                                     A blueberry-like, oriental,                                                   minty, camphoraceous, eucalyptol-like aroma                                   character with a camphora- ceous, oriental,                                   minty, eucalyp- tol flavor characteristic at                                  2 ppm making  it useful for oral hygiene and                                  cough drops flavors.                                                                   A sweet, woody, citrusy aroma with                                            cooling nuances prior to and on                                               smoking in the main- stream and in                                            the side- stream.                        Produced according                                                            to Example II                                                                 Mixture of:                                                                    ##STR105##                                                                             3,4,4A,5,8,8A- Hexahydro-2,2, 5,6 (and 7), 8A-tetramethyl- 1                  (2H)-naphtha- lenone (major- ity: "cis" isomer).                                       A green, her- baceous aroma with a lavender top-note                          and a basil/citrus undertone with bergamot-like                               nuances. A sweet, floral, musk-like, fresh rosey aroma                                 with a floral rosey flavor charac- teristic                                   at 0.2 ppm, causing it to be useful in rose                                   and raspberry flavors.                            Produced according                                                            to Example III                                                                Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR106##                                                                             Octahydro-2,2, 6 (and 7), 8A tetramethyl- 1 (2H)-naphtha-                     lenone (Major- ity: "cis" isomer).                                                     A peppery dry woody aroma with a precious woody back-                         ground and vetiver-like and ambery nuances.                                            An oriental black pepper- like, spicey aroma                                  with a black pepper flavor charac- teristic                                   at 1 ppm, causing it to be use- ful in black                                  pepper flavors.                                   produced according                                                            to Example IV                                                                 Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR107##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-2, 2,6 (& 7), 8A- tetrahydro-1-                  naphthol (Majority: "cis" isomer).                                                     A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                                            A citrus, fresh, musky, floral aroma with a                                   perfu- mery flavor characteristics at 0.1                                     ppm.                                              produced according                                                            to Example V                                                                  Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR108##                                                                             3,4,4A,5,8,8A- Hexahydro-2,2, 8 (and 5), 8A- tetramethyl- 1                   (2H)-naphtha- lenone (Major- ity: "cis" isomer).                                       A rich herba- ceous, lavender, thyme/rosemary aroma                           which  becomes sweaty on dry out.                                                      A floral, oriental, patchouli-like, camphorace                                ous, incense-like aroma charac- teristic with                                 n oriental, patchouli, camphoraceous flavor                                   profile at 2 ppm.                                                                      A sweet fruity, berry, cooling,                                               woody, floral aroma both prior to                                             and on smoking in the main stream                                             and in the side stream.                  Produced according                                                            to either of                                                                  Examples VI (A) or                                                            VI (B)                                                                         ##STR109##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-2, 2,8A-trimethyl- 1-naphthol.                            A patchouli, woody, campho- raceous aroma with a                              borneol- like undertone.                                                               A patchouli, camphoraceous, earthy aroma                                      characteristic with a patchouli, camphoraceous                                , earthy flavor characteristic at 1                                                    A sweet, woody, veti- ver-like aroma                                          and taste, both prior to and on                                               smoking in the main- stream and the                                           side- stream.                            Produced according                                                            to Example VII (A)                                                            or VII (B)                                                                    Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR110##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-2, 2,8 (and 5), 8A- tetramethyl-                 1-naphthol.                                                                            An intense patchouli- like aroma with a                                       woody background.                                                                      An oriental ionone-like, minty, eucalyp- tus,                                 cooling aroma with an oriental flavor                                         characteristic at 1 ppm                                                                A woody, patchouli- like, orien-                                              tal-like aroma both to and on                                                 smoking causing virginia- like                                                tobacco to attain a turkish tobacco                                           aroma and taste                          Produced according                                                            to Example VIII                                                               Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR111##                                                                             2,2,6 (and 7), 8A-tetramethyl- 1-naphthol                                              Sandalwood, patchouli-like aroma with incense-like                            undertones.                                                                            A sandalwood, patchouli, incense, ionoe and                                   eucalyptol aroma charac- ter with incense                                     flavor characteristics at 1 ppm.                  Produced according                                                            to Example IX                                                                  ##STR112##                                                                             Decahydro-2,2, 8A-trimethyl- 1-naphthol                                                An earthy, camphoraceous, woody, borneol- like,                               patchouli aroma with precious, woody undertones.                                       A minty, euca- lyptol-like, woody aroma                                       characteristic with minty eucalyptol-  like,                                  woody and bitter flavor charac- teristics at                                  0.1 ppm causing it to be useful for oral                                      hygiene flavors.                                  Produced according                                                            to Example X                                                                  Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR113##                                                                             Octahydro-2,2, 8,8A-tetra- methyl-1 (2H)- naphthalenone                                An earthy, camphoraceous, woody, borneol- like,                               patchouli aroma with precious, woody undertones                                        A minty, euca- lyptol-like woody aroma                                        characteristic with minty eucalyptol- like,                                   woody and bitter flavor charac- teristics at                                  0.1 ppm causing it to be useful for oral                                      hygiene flavors.                                                                       A sweet, woody aroma and taste both                                           prior to and on smoking.                 Produced according                                                            to Example XI                                                                  ##STR114##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-1,  2,2,8A-tetra- methyl-1-naph-                 thol.    A camphorace- ous/borneol, earthy, rooty, woody aroma                         with a patchouli background.                                                           An earthy, patchouli, oriental, walnut-like                                   aroma with an earthy patchouli oriental                                       walnut flavor characteris- tic causing it to                                  be useful in walnut fla- vors, at                                             a concentra- tion of 0.002 ppm                                                         A sweet, woody, veti- ver-like aroma                                          and taste both prior to and on                                                smoking in the main- stream and the                                           side- stream.                            Produced according                                                            to Example XII                                                                Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR115##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-1, 2,2,6 (and 7), 8A-pentamethyl-                1-naphthol (Majority: "cis" isomer).                                                   A dry woody, rooty, patchou- li aroma                                         with camphoraceous and borneol undertones.                                             A patchouli, oriental and earthy aroma                                        characteris- tic with a patchouli earthy                                      flavor characteris- tic making it useful for                                  walnut flavors at 1 ppm                           produced according                                                            to Example XIII                                                               Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR116##                                                                             1,2,3,4,4A,5,8, 8A-Octahydro-1, 2,2,8 (and 5), 8A-pentamethyl-                1-naphthol.                                                                            A patchouli aroma with minty top- notes.                                               An oriental, ionone-like, minty, euca-                                        lyptol-like, patchouli-like aroma with a                                      patchouli-like flavor charac- teristic at 1                                   ppm      A woody, patchouli- like aroma and                                            taste both prior to and on smoking                                            yielding a cigar-type taste in the                                            main- stream and the side- stream.       Produced according                                                            to Example XIV                                                                 ##STR117##                                                                             Decahydro-1,2, 2,8A-tetra- methyl-1-naph- thol.                                        A patchouli aroma with minty top- notes.                                               An oriental ionone-like, minty, euca-                                         lyptol-like, patchouli-like aroma with a                                      patchouli-like flavor charac- teristic at 1                                   ppm.                                              Produced according                                                            to Example XV                                                                 Mixture of:                                                                    ##STR118##                                                                             Decahydro-1,2, 2,8 (and 5), 8A- pentamethyl- 1-naphthol                                                  A woody, camphoraceous, and                                                   patchouli- like aroma and taste both                                          prior to and on smoking with woody,                                           oriental notes in the smoke flavor                                            causing it to be use- ful in the                                              production of Turkish toba- cco                                               flavor, this material imparts a                                               Turkish toba- cco aroma and taste                                             nuance to Virginia tobaccos in both                                           the main- stream and  the side-                                               streams.                                 Prepared by                                                                   reacting                                                                      CH.sub.3 Li with                                                              product of                                                                    Example XI                                                                    Mixture of                                                                    compounds having                                                              the structures:                                                                ##STR119##                                                                             Decahydro-1,2, 2,6 (and 7), 8A- pentamethyl- 1-naphthol.                               An earthy, camphoreceous aroma with patchouli backgroun                       d.       A patchouli, camphoraceous aroma and flavor                                   pro- file at 2 ppm.                                                                    A woody, patchouli- like aroma and                                            taste both prior to and on smoking.      Prepared according                                                            to Example XVI                                                                __________________________________________________________________________

When the methyl substituted oxobicyclo-4,4,0-decane derivatives of ourinvention are used as food flavor adjuvants, the nature of theco-ingredients included with each of the said methyl substitutedoxobicyclo-4,4,0-decane derivatives in formulating the productcomposition will also serve to alter, modify, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs, include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to means a composition whichcomprises a substantially water-insoluble, chewable plastic gum basesuch chicle, or substitutes therefor, including jelutong, guttakay,rubber or certain comestible natural or synthetic resins or waxes.Incorporated with the gum base in admixture therewith may beplasticizers or softening agents, e.g., glycerine; and a flavoringcomposition which incorporates one or more of the methyl substitutedoxobicyclo-4,4,0-decane derivatives of our invention, and in addition,sweetening agents which may be sugars, including sucrose or dextroseand/or artificial sweeteners such as cyclamates or saccharin. Otheroptional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectines, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents includes emulsifying agents, e.g., fatty acidssuch as capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g. benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like;starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anticaking agents, e.g., aluminumcalcium sulfate and tribasic calsium phosphate; enzymes; yeast foods,e.g., calcium lactate and caldium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta,beta-dimethylacrolein, methyl n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, damascone, α-damascone, damascenone,acetophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methylfurfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol , 3-methyl-3-buten-1ol, 1-pentanol,1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpin hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl carpylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alphamethylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyldiphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, α-phellandrene, β-phellandrene, p-cymene 1-alpha-pinene,beta-pinene, dihydrocarveol; pyrazines such as 2,3-dimethylpyrazine,2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oilssuch as jasmine absolute, cassia oil, cinnamon bark oil, black pepperoleoresin, oil of black pepper, rose absolute, orris absolute, oil ofcubeb, oil of coriander, oil of pimento leaf, oil of patchouli, oil ofnutmeg, lemon essential oil, safran oil, Bulgarian rose, capsicum, yarayara and vanilla; lactones such as γ-nonalactone; sulfides, e.g., methylsulfide and other materials such as maltol, and acetal (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane), piperine,chavicine, and piperidine.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the methyl substitutedoxobicyclo-4,4,0-decane derivatives of our invention by not covering orspoiling the organoleptic properties (aroma and/or taste) thereof; (ii)be non-reactive with the methyl substituted oxobicyclo-4,4,0-decanederivatives of our invention and (iii) be capable of providing anenvironment in which the methyl substituted oxobicyclo-4,4,0-decanederivatives can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositons, ingredient selection will vary in accordance withthe foodstuff, chewing gum, medicinal product or toothpaste to which theflavor and/or aroma are to be imparted, modified, altered or enhanced.In contradistinction, in the preparation of solid products, e.g.,simulated foodstuffs, ingredients capable of providing normally solidcompositions should be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of methylsubstituted oxobicyclo-4,4,0-decane derivatives employed in a particularinstance can vary over a relatively wide range, depending upon thedesired organoleptic effects to be achieved. Thus, correspondingly,greater amounts would be necessary in those instances wherein theultimate food composition to be flavored is relatively bland to thetaste, whereas relatively minor quantities may suffice for purposes ofenhancing the composition merely deficient in natural flavor or aroma.The primary requirement is that the amount selected to be effective,i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition, whether foodstuff per se,chewing gum, per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of methyl substitutedoxobicyclo-4,4,0-decane derivatives will, of course, substantiallyvitiate any possibility of obtaining the desired results while excessquantities prove needlessly costly and, in extreme cases, may disruptthe flavor-aroma balance, thus proving self-defeating. Accordingly, theterminology "effective amount" and "sufficient amount" is to be accordeda significance in the context of the present invention consistent withthe obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpaste compositons,it is found that quantities of methyl substitutedoxobicyclo-4,4,0-decane derivatives ranging from a small but effectiveamount, e.g., 0.01 parts per million up to about 100 parts per millionbased on total composition are suitable. Concentrations in excess of themaximum quantity stated are not normally recommended, since they fail toprove commensurate enhancement of organoleptic properties. In thoseinstances, wherein the methyl substituted oxobicyclo-4,4,0-decanederivatives are added to the foodstuff as an integral component of aflavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective methyl substituted oxobicyclo-4,4,0-decane derivativeconcentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the methyl substitutedoxobicyclo-4,4,0-decane derivatives in concentrations ranging from about0.01% up to about 15% by weight based on the total weight of the saidflavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formualted by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of disperseion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the methyl substitutedoxobicyclo-4,4,0-decane derivatives with, for example, gum arabic, gumtragacanth, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powdermix are obtained by mixing the dried solid components, e.g., starch,sugar and the like and methyl substituted oxobicyclo-4,4,0-decanederivatives in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the methyl substitutedoxobicyclo-4,4,0-decane derivatives of our invention, the followingadjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenyl acetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl Hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate;

Cassia oil;

Vanillin;

Maltol;

Parahydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute;

Terpenyl acetate;

Gamma-undecalactone;

Vanilla;

Alcohol;

Oil of Cubeb;

Phellandrene;

β-phellandrene;

Oil or Coriander;

Oil of Pimento Leaf;

Oil of Patchouli;

Alpha Pinene;

Beta Pinene;

Beta-caryophyllene;

Dihydrocarveol;

Piperonal;

Piperine;

Chavicine;

Piperidine;

Oil of Black Pepper;

Black Pepper Oleoresin;

Capsicum;

Oil of Nutmeg;

Cardamom Oil;

Clove Oil;

Spearmint Oil; and

Oil of Peppermint.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which specific desired sweet, fruity, berry-like, woodyand floral flavor characteristics of natural tobacco (prior to smokingand, on smoking, in the mainstream and in the sidestream) as well ascooling effects, are created or enhanced or modified or augmented andmay be readily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable natural aromatic tobacco flavoringcharacteristics with sweet, fruity, berry-like, cooling, woody andfloral notes may be imparted to smoking tobacco products and may bereadily varied and controlled to produce the desired uniform flavoringcharacteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substituted therefor (e.g., dried lettuceleaves) an aroma and flavor additive containing as an active ingredientone or more methyl substituted oxobicyclo-4,4,0-decane derivatives ofour invention.

In addition to the methyl substituted oxobicyclo-4,4,0-decanederivatives or our invention other flavoring and aroma additives may beadded to the smoking tobacco material or substitute therefor eitherseparately or in mixture with the methyl substitutedoxobicylo-4,4,0-decane derivatives as follows:

I. Synthetic Materials

Beta-ethyl-cinnameldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee Extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil; and

Origanum Oil.

An aroma and flavoring concentrate containing one or more methylsubstituted oxobicyclo-4,4,0-decane derivatives of our invention and, ifdesired, one or more of the above indicated additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper. The smoking tobacco material may beshredded, cured, cased and blended tobacco material or reconstitutedtobacco material or tobacco substitutes (e.g., lettuce leaves) ormixtures thereof. The proportions of flavoring additives may be variedin accordance with taste but insofar as enhancement or the imparting ofnatural and/or sweet notes and/or cooling notes and/or fruity notesand/or woody notes, we have found that satisfactory results are obtainedif the proportion by weight of the sum total of methyl substitutedoxobicyclo-4,4,0-decane derivative(s) to smoking tobacco material isbetween 50 ppm and 1,500 ppm (0.015%-0.15%). We have further found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of methyl substituted oxobocyclo-4,4,0-decane derivative used toflavoring material is between 1,500 and 15,000 ppm (0.15%-1.5%).

Any convenient method for incorporating the methyl substitutedoxobicyclo-4,4,0-decane derivative(s) into the tobacco product may beemployed. Thus, the methyl substituted oxobicyclo-4,4,0-decanederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, diethyl ether and/orvolative organic solvents and the resulting solution may either bespread on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the methyl substituted oxobicyclo-4,4,0-decanederivative(s) taken alone or taken further together with other flavoringadditives as set forth above, may be applied by means of a suitableapplicator such as a brush or roller on the paper or leaf wrapper forthe smoking product, or it may be applied to the filter by eitherspraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the methylsubstituted oxobicyclo-4,4,0-decane derivative(s) in excess of theamounts or concentrations above indicated so that when blended withother tobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of3,4,4A,5,8,8A-hexahydro-2,2,5,8A-tetramethyl-1-(2H)-naphthalenoneprepared according to Example VI(B), in an amount to provide a tobaccocomposition containing 800 ppm by weight of3,4,4A,5,8,8A-hexahydro-2,2,5,8A-tetramethyl-1-(2H)-naphthalenone on adry basis. Thereafter, the alcohol is removed by evaporation and thetobacco is manufactured into cigarettes by the usual techniques. Thecigarette when treated as indicated has a desired and pleasing aromawhich is detectable in the main and sidestreams when the cigarette issmoked. This aroma is described as being sweeter, more aromatic, moretobacco-like and having a sweet, fruity note.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the methyl substituted oxobicyclo-4,4,0-decanederivative(s) of our invention can be incorporated with materials suchas filter tip materials (e.g. cellulose acetate filters wherein sweet,woody, fruity, floral and/or cooling effects are desired), seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, the methyl substitutedoxobicyclo-4,4,0-decane derivative(s) can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The methyl substituted oxobicyclo-4,4,0-decane derivative(s) and one ormore auxiliary perfume ingredients, including, for example,hydrocarbons, alcohols, ketones, aldehydes, nitriles, esters, lactonesor cyclic esters, synthetic essential oils and natural essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferably insandalwoody and/or patchouli-like fragrances. Such perfume compositionsusually contain (a) the main note or the "bouquet" or foundation stoneof the compositon; (b) modifiers which round off and accompany the mainnote; (c) fixatives which include odorous substances which lend aparticular note to the perfume throughout all stages of evaporation andsubstances which retard evaporation; and (d) top-notes which are usuallylow boiling fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the methyl substituted oxobicyclo-4,4,0-decane derivative(s) of ourinvention can be used to alter, modify or enhance the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of methyl substituted oxobicyclo-4,4,0-decane derivative(s)of our invention which will be effective in perfume compositions as wellas in perfumed articles and colognes depends on many factors, includingthe other ingredients, their amounts and the effects which are desired.It has been found that perfume compositions containing as little as0.01% of methyl substituted oxobicyclo-4,4,0-decane derivative(s) oreven less (e.g. 0.005%) can be used to impart a minty, camphoraceous,dry, woody, sweet, fruity, patchouli-like, woody patchouli, green,herbaceous, basil-like, citrus-like, bergamot-like, lime-like,grapefruit-like, peppery, precious woody, vertiver-like, fresh, musky,lavander, thyme, rosemary, sweaty, rooty and earthy nuances with floral,citrus, lavander and amber topnotes to soaps, cosmetics, detergents(including anionic, non-ionic, cationic and zwitterionic solid or liquiddetergents) or other products. The amount employed can range up to 70%of the fragrance components and will depend on considerations of cost,nature of the end product, the effect desired on the finished productand the particular fragrance sought.

The methyl substituted oxobicyclo-4,4,0-decane derivative(s) of ourinvention are useful (taken alone or together with other ingredients inperfume compositions) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, hair preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as, creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, face powders and the like. As little as 0.1%of the methyl substituted oxobicyclo-4,4,0-decane derivative(s) willsuffice to impart an intense minty, camphoraceous, dry woody, sweetfruity, patchouli, woody patchouli, green, herbaceous, basil-like,citrus-like, bergamot-like, lime-like, graperfruit-like, peppery,precious woody, vertiver-like, fresh, musky, lavander, thyme, rosemary,sweaty, rooty and/or earthy aroma to woody perfume formulations.Generally, no more than 5% of the methyl substitutedoxobicyclo-4,4,0-decane derivative(s) based on the ultimate end product,is required in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the methyl substitutedoxobicyclo-4,4,0-decane derivative(s). The vehicle can be a liquid suchas a non-toxic alcohol, a non-toxic glycol, or the like. The carrier canalso be an absorbent solid, such as gum (e.g., gum arabic), orcomponents for encapsulating the composition (such as gelatin).

It will thus be apparent that the methyl substitutedoxobicyclo-4,4,0-decane derivative(s) of our invention can be utilizedto alter, modify or enhance sensory properties, particularlyorganoleptic properties, such as flavor(s) and/or fragrance(s) of a widevariety of consumable materials.

The following Examples serve to illustrate processes for specificallyproducing the methyl substituted oxobicyclo-4,4,0-decane derivatives ofour invention and also serve to illustrate specific embodiments of ourinvention.

It will be understood that these Examples are illustrative and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF3,4,4A,5,8,8A-HEXAHYDRO-2,2,8A-TRIMETHYL-1(2H)-NAPHTHALENONE Reaction##STR120##

483.0 g (3.5 moles) of 2,6,6-trimethyl-2-cyclohexenone-1, 48.0 g (0.36moles) of aluminum chloride and 200 cc of anhydrous toluene are combinedat room temperature. When the exotherm ceases, the reaction mass iscooled to 0° C. The mixture of cyclohexenone, toluene and aluminumchloride is placed in an autoclave. The contents of the autoclave arecooled to 0° C. and the butadiene (216 g, 4.0 moles) is added. Theautoclave is closed immediately and set to operate at room temperaturefor 6 hours. At the end of the 6 hour period, substantially nocyclohexenone remains. The reaction mass is then transferred to aseparatory funnel whereupon water is added and sufficient acetic acid isadded to give good separation. The organic layer is washed with two 200cc volume of sodium bicarbonate. The reaction mass is then stripped anddistilled on a one-plate distillation column to yield 429 g of product(64% of theory) with the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        70/77    95/100    1.5/1.5                                                                              17.0                                       2        85      103        1.4    44.0                                       3        90      110        1.4    95.0                                       4        90      111        1.4    97.0                                       5        90      115        1.4    93.0                                       6        92      167        2.0    83.0                                       ______________________________________                                    

NMR, IR and mass spectral analysis yield the information that theresulting product has the structure: ##STR121##

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR122##

FIG. 2 is the mass spectrum for the product of Example I having thestructure: ##STR123##

FIG. 3 represents the NMR spectrum for the product of Example I havingthe structure: ##STR124##

FIG. 4 represents the infrared spectrum for the product of Example Ihaving the structure: ##STR125##

EXAMPLE II PREPARATION OF OCTAHYDRO-2,2,8A-TRIMETHYL-1(2H)-NAPHTHALENONEReaction ##STR126##

Into a shaker-type pressure vessel (Parr® shaker) is placed 50.5 g ofthe ketone produced according to Example I having the structure:##STR127## 0.6 g of a 10% palladium on carbon catalyst and 50 mliso-propyl alcohol. The pressure vessel is closed and pressurized withhydrogen to a pressure of 50 psig and maintained at that pressure for aperiod of 1.3 hours. At the end of the 1.3 hour period the pressurevessel is opened and the contents filtered. The filtrate is stripped ofsolvent (iso-propyl alcohol) and then distilled using amicrodistillation apparatus yielding the following fractions:

    ______________________________________                                                 Vapor        Liquid                                                  Fraction Temp.        Temp.    mm/Hg.                                         No.      (°C.) (°C.)                                                                           Pressure                                       ______________________________________                                        1        98/99        102/102  3.0/3.0                                        2        100          104      3.0                                            3        99           105      3.0                                            4        80           104      3.0                                            5        99           110      3.0                                            6        99           140      3.0                                            7        80           240      3.0                                            ______________________________________                                    

The yield is 89%, with fractions 1-6 bulked.

NMR, IR and mass spectral analysis yield the information that theresulting product has the structure: ##STR128##

FIG. 5 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR129##

FIG. 6 is the mass spectrum for the product of Example II having thestructure: ##STR130##

FIG. 7 is the NMR spectrum for the product of Example II having thestructure: ##STR131##

FIG. 8 is the infrared spectrum for the product of Example II having thestructure: ##STR132##

EXAMPLE III PREPARATION OF 3,4,4A,58,8A-HEXADYDRO-2,2,6(and 7),8A-TETRAMETHYL-1-(2H)NAPHTHALONE Reaction ##STR133##

At room temperature, 69 g (0.5 moles) of 2,6,6-cyclohexenone is admixedwith 6.7 g (0.05 moles) of aluminum trichloride. The reaction massexoterms to 44° C. and is cooled. The reaction mass is cooled to 22° C.and over a period of 10 minutes 34 g (0.5 moles) of isoprene is added tothe reaction mixture. The reaction mass is stirred at room temperaturewith cooling for a period of of 1 hour. 0.5 moles additional isoprene isthen added. The reaction mass is stirred for an additional hour. At theend of this hour, 150 ml water is added. The reaction mass is thenwashed as follows:

a. two 250 ml volumes of water

b. two volumes of saturated sodium carbonate

c. one 250 ml volume of saturated sodium chloride solution.

All aqueous layers are combined and extracted with 150 ml toluene. Theextract is washed with saturated sodium chloride and the extract and oillayers are then combined and washed with two 250 ml volume of 10% sodiumchloride. The oil and aqueous layers are separated and the oil layer isdried over anhydrous sodium sulfate. The resulting material is filteredand then distilled on an one-plate distillation column giving 69 g ofproduct (67% yield) with b.p. of 102°-104° C./3 mmHg.

NMR, IR, and mass spectral analysis yield the information that theresulting product is a mixture of compounds having the structures:##STR134##

FIG. 9 is the GLC profile for the reaction product of Example IIIcontaining the compounds having the structures: ##STR135## (fraction 2of one-plate distallation, "Rushover")

FIG. 9A represents the GLC profile for the major product of Example III.

FIG. 10 is the mass spectrum for the product of Example III having thestructures: ##STR136##

FIG. 11 is the NMR spectrum for the product of Example III having thestructures: ##STR137##

FIG. 12 is the infrared spectrum for the product of Example III havingthe structures: ##STR138##

EXAMPLE IV PREPARATION OF OCTAHYDRO-2,2,6(and 7),8A,TETRAMETHYL-1-1(2H)-NAPHTHALENONE Reaction ##STR139##

Into a hydrogenation pressure vessel is placed 84 g of the ketonemixture produced according to Example III containing compounds havingthe structures: ##STR140## (0.41 moles); 0.5 grams of a 10% palladium oncarbon catalyst and 100 ml of isopropyl alcohol. The pressure vessel isclosed and with shaking the hydrogen pressure is build up to 44-50 psig.Hydrogen pressure is maintained for a period of 9.3 hours. At the end ofthe 9.3 hour period the pressure vessel is opened and the contents arefiltered and stripped of solvent. The resulting oil is then distilled ina microdistillation apparatus yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        97/100  109/107    3.0    3.5                                        2        100     110        3.0    13.7                                       3        100     115        3.0    10.9                                       4        102     122        3.0    23.3                                       5        100     165        3.0    6.8                                        ______________________________________                                    

Fractions 1-5 are bulked. The yield is 95%.

NMR, IR and mass spectral analysis yield the information that theresulting product contains the compounds having the structures:##STR141##

FIG. 13A is the GLC profile for the reaction mixture of Example IV(fraction 3, "cis-isomer") containing the compounds having thestructures: ##STR142##

FIG. 13B is the GLC profile for the reaction mixture of Example IVspiked with reactant and thus containing the compounds having thestructures: ##STR143##

FIG. 14 is the mass spectrum for the reaction product of Example IV,fraction 3, containing the compounds having the structures: ##STR144##

FIG. 15 is the NMR spectrum for the reaction product of Example IV,containing the compounds having the structures: ##STR145##

FIG. 16 is the infrared spectrum for the reaction product of Example IV,fraction 3, containing the compounds having the structures: ##STR146##

EXAMPLE V PREPARATION OF1,2,3,4,4A,5,8,8A-OCTAHYDRO-2,2,6(&7),8A-TETRAHYDRO-1-NAPHTHOL Reaction##STR147##

Into a reaction flask equipped with stirrer thermometer and refluxcondenser, place 75 g (0.36 moles) of the product of Example IIIcontaining the compounds having the structures: ##STR148## and 50 mlisopropyl alcohol. Then, a mixture of 5.1 g (0.13 moles) of sodiumborohydride and 50 ml of isopropyl alcohol is added at room temperature.

The reaction mass is stirred for a period of 5 hours at room temperatureand then for a period of 3 hours at 77° C. The reaction is then quenchedby adding the reaction mass to 10% acetic acid, aqueous solution. Theaqueous phase is separated from the organic phase and the organic phaseis washed with saturated sodium carbonate solution and then 10% sodiumchloride solution. The organic phase is then dried over anhydrous sodiumsulfate and fractionated on a microdistillation apparatus yielding thefollowing fractions:

    ______________________________________                                                Vapor    Liquid            Weight of                                  Fraction                                                                              Temp.    Temp.      mm/Hg  Fraction                                   No.     (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1       27/25     43/105    3.0/3.0                                                                              3.7                                        2        47/102  104/112    3.0    2.7                                        3       113      127        3.0    3.6                                        4       121      135        3.0    10.7                                       5       121      140        3.0    5.7                                        6       121      145        3.0    5.0                                        7       118      147        3.0    5.9                                        8       108      167        3.0    14.9                                       9        90      245        3.0    7.6                                        ______________________________________                                    

Fractions 4-7 are bulked (yield is 49%).

NMR, IR and mass spectral analysis yield the information that theresulting product is a mixture of compounds having the structures:##STR149##

FIG. 17 is the GLC profile for the reaction product of Example Vcontaining the compounds having the structures: ##STR150##

FIG. 18 is the mass spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR151##

FIG. 19 is the NMR spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR152##

FIG. 20 is the infrared spectrum for the reaction product of Example Vcontaining the cis-isomer of the compounds having the structures:##STR153##

EXAMPLE VIA PREPARATION OF 3,4,4A,5,8,8A-HEXAHYDRO-2,2,8(and5),8A-TETRAMETHYL-1-(2H)-NAPHTHALENONE Reaction ##STR154##

Into a reaction flask equipped with thermometer, reflux condenser andcooling bath is placed 69 g (5 moles) of 2,6,6-trimethyl cyclohexenone.Over a period of 17 minutes with cooling while maintaining the reactionmass at 10° C.-25° C., 6.7 g (0.05 moles) of aluminum trichloride isadded thereto. Then, 34 g (0.5 moles) of piperylene (1,3-pentadiene) isthen added to the reaction mass with cooling over a period of one hour.The reaction mass is then stirred for a period of one hour at atemperature of 25° C. 100 ml of 10% aqueous hydrochloric acid is thenadded to the reaction mass with cooling. The aqueous phase is separatedfrom the organic phase and toluene is added thereto. The organic layeris then washed with 100 ml 10% aqueous sodium chloride followed by 10%aqueous sodium hydroxide. The resulting material is then dried overanhydrous sodium sulfate, admixed with sodium bicarbonate, in order toscavange any acid present. The resulting product is filtered and thesolvent is stripped off.

The resulting material is fractionally distilled on a six inchmicrodistillation column to yield the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     mm/Hg  Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (g.)                                       ______________________________________                                        1         36/90   77/108    3.0/3.0                                                                              14.5                                       2          99     112       3.0    4.8                                        3         101     115       3.0    7.3                                        4         102     112       3.0    8.4                                        5         102     116       3.0    5.2                                        6         103     119       3.0    11.8                                       7         103     126       3.0    11.4                                       8         103     158       3.0    11.2                                       9          90     220       3.0    6.1                                        ______________________________________                                    

Fractions 2-8 are bulked (yield: 61%).

NMR, IR and spectral analysis yield the information that the resultingproduct is a mixture of the compounds having the structures: ##STR155##

FIG. 21 is the GLC profile for the reaction product of Example VI(A),fraction 7, containing the compounds having the structures: ##STR156##

FIG. 22 is the mass spectrum for the reaction product of Example VI(A),fraction 7, containing the compounds having the structures: ##STR157##

FIG. 23 is the NMR spectrum for the reaction product of Example VI(A)containing the compounds having the structures: ##STR158##

FIG. 24 is the infrared spectrum for the reaction product of ExampleVI(A) containing the compounds having the structures: ##STR159##

EXAMPLE VIB PREPARATION OF 3,4,4A,5,8,8A-HEXAHYDRO-2,2,8(and5),8A-TETRAMETHYL-1-(2H)-NAPHTHALENONE Reaction ##STR160##

Into a 5 liter reaction flask equipped with stirrer, condenser,thermometer and dropping funnel is placed 200 cc toluene. 33.5 g (0.25moles) of aluminum chloride is then added. 345 g (2.5 moles) of2,6,6-cyclohexenone is then added dropwise to the reaction mass whichexotherms to 35° C. The reaction mass is cooled to room temperature and340.0 g (5.0 moles) of piperylene is added dropwise maintaining thetemperature at 25° C. The reaction mass is then stirred at roomtemperature for a period of six hours while being monitored by GLC tocompletion (conditions: SE 30, column programmed at 100°-150° C. at 8°C. per minute). The reaction mass is then "worked up" by adding water,stirring and separating the layers. The organic layer is then washedwith one 1000 cc volume of water stipped and distilled to yield 414 g ofproduct (80% of theory). The distillation is carried out on a 12inch-packed column (stone) yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        56/70   100/110    2.0/2.8                                                                              33.0                                       2         80     120        0.8    32.0                                       3        100     125        0.8    64.0                                       4        102     126        0.8    77.0                                       5        102     130        0.8    90.0                                       6        101     140        0.5    67.0                                       7         94     172        0.5    41.0                                       8         80     230        0.5    70.0                                       ______________________________________                                    

Fractions 3-7 are bulked.

NMR, IR and mass spectral analysis yield the information that theresulting product is a mixture of compounds having the structures:##STR161##

FIG. 25 sets forth the GLC profile for bulk fractions 2-7 for theforegoing distillation.

EXAMPLE VIIA PREPARATION OF1,2,3,4,4A,5,8,8A-OCTAHYDRO-2,2,8A-TRIMETHYL-1-NAPHTHOL Reaction##STR162##

Into a reaction flask, equipped with stirrer, thermometer, refluxcondenser and cooling bath, is placed 50 ml anhydrous isopropyl alcoholand 45.4 g (0.12 moles) of 12% sodium borohydride aqueous sodium. Over aperiod of five minutes the ketone reaction product of Example I (245 g;1.28 moles) having the structure: ##STR163## is added to the reactionmass. The reaction mass is then heated to 88° C. and maintained at thattemperature for a period of 8 hours. The resulting reaction product ispoured into 100 ml of water and extracted with 50 ml of diethyl ethertwice. The organic layer is washed with satured sodium chloride solutionand dried over anhydrous sodium sulfate. Stripping of the solvent gives17 g of crystalline product (85% yield). The crude product isrecrystallized from hexane giving pure product having a m.p. 58°-59° C.

    ______________________________________                                                 Vapor        Liquid                                                  Fraction Temp.        Temp.    mm/Hg                                          No.      (°C.) (°C.)                                                                           Pressure                                       ______________________________________                                        1        97/105       114/120  4.0/3.2                                        2        111          157      3.0                                            3        114          235      3.0                                            ______________________________________                                    

NMR, IR and mass spectral analysis yield the information that theresulting product has the structure: ##STR164##

FIG. 26A is the GLC profile for the crude product of the reaction ofExample VII(A) containing the compound having the structure: ##STR165##

FIG. 26B is the GLC profile for bulked fractions 1-3 of the distillationproduct of the reaction product of Example VII(A) containing thecompound having the structure: ##STR166##

FIG. 27 is the mass spectrum for the reaction product of Example VII(A),bulked fractions 1-3, containing the compound having the structure:##STR167##

FIG. 28 is the NMR spectrum for the reaction product of Example VII(A),bulked fractions 1-3, containing the compound having the structure:##STR168##

FIG. 29 is the infrared spectrum for the reaction product of ExampleVII(A), bulked fractions 1-3, containing the compound having thestructure: ##STR169##

EXAMPLE VIIB PREPARATION OF1,2,3,4,4A,5,8,8A-OCTAHYDRO-2,2,8A-TRIMETHYL-1-NAPHTHOL Reaction##STR170##

Into a 250 cc reaction flask equipped with stirrer, condenser,thermometer, dropping funnel and nitrogen inlet tube, to provide anitrogen blanket, is placed 60 cc (0.15 moles) of 2.5 M solution ofisopropyl magnesium chloride in diethyl ether. The grignard reagentsolution is cooled to 10° C. and dropwise over a period of 5 minutes,19.2 g (0.1 moles) of the ketone having the structure: ##STR171##prepared according to Example I is added. The reaction mass exotherms to30° C. The reaction mass is refluxed for a period of 1.5 hours whereuponGLC analysis indicates completion of the reaction (conditions: SE 30,column programed at 150° C. at 8° C. per minute). The reaction mass isthe hydrolyzed with 20 cc of an ammonium chloride solution. The organicphase is separated from the aqueous phase, dried, stripped and distilledon a one-plate column to yield 17 g of crystals having b.p. 100°-114°C./2 mmHg pressure.

The resulting material as confirmed by GLC, IR, and mass spectralanalysis has the structure: ##STR172##

FIG. 30 is the GLC profile for the reaction product after 1.5 hours.

FIG. 31 represents the GLC profile for the reaction product spiked withreactant ketone having the structure: ##STR173##

EXAMPLE VIII PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO-2,2,8(and5),8A-TETRAMETHYL-1-NAPHTHOL Reaction ##STR174##

Into a 500 cc reaction flask equipped with stirrer, condenser,thermometer and dropping funnel, 20.7 g (0.55 moles) of lithium aluminumhydride and 50 cc of tetrahydrofuran are added. Dropwise over a periodof 5 minutes, 114.0 g (0.55 moles) of the mixture of ketone having thestructures: ##STR175## prepared according to Example VIA is added whilemaintaining the reaction mass at 10°-20° C.

After addition of the mixture of ketones, the reaction mass is stirredat 25° C. for a period of one hour. At the end of the one hour period,GLC analysis indicates that the reaction is complete, there being nostarting material present.

The resulting lithium salt reaction product is then hydrolyzed using 20cc of a 0.4 molar ammonium chloride solution. The resulting two phases,the aqueous phase and the organic phase are separated and the organicphase is dried over anhydrous sodium sulfate, stripped of solvent anddistilled on a one plate column yielding 45 g of products (43% oftheory). The product is then distilled on a 12-inch stonepack columnyielding the following fractions:

    ______________________________________                                                Vapor    Liquid            Weight of                                  Fraction                                                                              Temp.    Temp.      mm/Hg  Fraction                                   No.     (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1       80/95    110/115    1.5/1.0                                                                              2.0                                        2       105      115        1.0    9.0                                        3       105      120        0.9    24.0                                       4       105      200        0.9    7.0                                        ______________________________________                                    

NMR, IR and mass spectral analysis yield the information that theproduct is a mixture of compounds having two structures: ##STR176##

FIG. 32 is the GLC profile for the reaction product of Example VIIIcontaining the compounds having the structures: ##STR177##

FIG. 33 is the mass spectrum for the reaction product of Example VIIIcontaining the compounds having the structures: ##STR178##

FIG. 34 is the NMR spectrum for the reaction product of Example VIII,fraction 3, containing the compounds having the structures: ##STR179##

FIG. 35 is the infrared spectrum for fraction 3 of the distillationproduct of the reaction product of Example VIII containing the compoundshaving the structures: ##STR180##

EXAMPLE IX PREPARATION OF 2,2,6,(and 7),8A-TETRAMETHYL-1-NAPHTHOLReaction ##STR181##

Into a 500 cc reaction flask equipped with stirrer, condenser,thermometer and dropping funnel are placed 100 cc of tetrahydrofuran and16.23 g (0.408 moles) of 95% lithium aluminum hydride thereby forming aslurry. While maintaining the temperature of the slurry at 10°-20° C.,and over a 20 minute period, 85 g (0.408 moles) of the mixture ofketones having the structures: ##STR182## prepared according to ExampleIV. After addition the reaction mass is stirred at room temperature fora period of 1.5 hours at the end of which time GLC analysis and IRanalysis indicates that the reaction is complete.

200 cc of water are then added to the reaction mass with cooling. Thereaction mass is then extracted with two 100 cc portions of toluene. Thetoluene extract is then stripped (of toluene) and the residue isdistilled yielding 81.5 g (96% of theory) of product, confirmed by IR,mass spectral analysis and NMR analysis to be a mixture of compoundshaving the structures: ##STR183##

The distillation is carried out using microdistillation apparatusyielding the following fractions:

    ______________________________________                                                Vapor    Liquid            Weight of                                  Fraction                                                                              Temp.    Temp.      mm/Hg  Fraction                                   No.     (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1       120/120  122/125    0.6/0.6                                                                              12.0                                       2       120      125        0.6    17.0                                       3       120      125        0.6    15.0                                       4       120      125        0.6    14.0                                       5       120      188        0.6    24.0                                       ______________________________________                                    

FIG. 36 is the GLC profile for the reaction product of Example IXcontaining the compounds having the structures: ##STR184##

FIG. 37 is the mass spectrum for the reaction product of Example IXcontaining the compounds having the structures: ##STR185##

FIG. 38 is the NMR spectrum for the distillation product, fraction 4, ofthe reaction product of Example IX containing the compounds having thestructures: ##STR186##

FIG. 39 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example IX containing the compoundshaving the structures: ##STR187##

EXAMPLE X PREPARATION OF DECAHYDRO-2,2,8A-TRIMETHYL-1-NAPHTHOL Reaction##STR188##

Into a 500 cc reaction flask fitted with stirrer, condenser,thermomether and dropping funnel is placed 14.8 g (0.39 moles) oflithium aluminum hydride in 70 cc of tetrahydrofuran. To the resultinglithium aluminum hydride slurry, dropwise, is added 76.0 g (0.39 moles)of the ketone having the structure: ##STR189## prepared according toExample II. The reaction mass is stirred at room temperature for aperiod of 3 hours. At the end of the 3 hour period, IR and GLC analysisindicate completion of the reaction. To the resulting reaction mass 100cc of 0.4 molar acetic acid is added. The organic phase is separatedfrom the aqueous phase and the organic phase is washed with two 50 ccsaturated sodium bicarbonate solution portions. The resulting materialis then dried over anhydrous sodium sulfate, stripped of solvent anddistilled on a one-plate column. The resulting product is thenredistilled on a 12 inch stone-packed column to yield the followingfractions: (yield 86%).

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     mm/Hg  Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (g.)                                       ______________________________________                                        1         75/80   90/190    0.8/0.7                                                                              20.0                                       2         80      180       0.7    46.0                                       ______________________________________                                    

The total yield is 66.0 g (86.0% yield). The resulting product has thestructure: ##STR190##

FIG. 40 is the GLC profile for the reaction product of Example X,containing the compound having the structure: ##STR191##

FIG. 41 is the mass spectrum for the reaction product of Example X,containing the compound having the structure: ##STR192##

FIG. 42 is the NMR spectrum for fraction 1 of the distillation productof the reaction product of Example X, containing the compound having thestructure: ##STR193##

FIG. 43 is the infrared spectrum for fraction 1 of the distillationproduct of the reaction product of Example X, containing the compoundhaving the structure: ##STR194##

EXAMPLE XI PREPARATION OFOCTAHYDRO-2,2,8,8a-TETRAMETHYL-1-(2H)-NAPHTHALENONE Reaction ##STR195##

Into an autoclave is charged the following materials:

2.85 g of 10% palladium on carbon catalyst

200 cc isopropyl alcohol

114.0 g (0.55 moles) of the mixture of ketones having the structures:##STR196## prepared according to Example VI(A).

At room temperature over a period of two hours while maintaining thepressure at 200 psig hydrogen is continually charged to the autoclave.

At the end of the two hour period, the autoclave is opened and thereaction mass is filtered over Supercell®. The reaction mass is thenstripped of solvent and distilled on a one-plate column yielding 104.0 g(91% of theory) of a mixture of compounds having the structures:##STR197##

The resulting product is then distilled on a 12 inch stone-packed columnyielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        70/85   100/105    1.8/1.8                                                                              4.0                                        2        85      115        0.7    19.0                                       3        92      117        0.7    17.0                                       4        95      118        0.7    32.0                                       5        95      140        0.7    36.0                                       ______________________________________                                    

Fractions 2-5 are product, 91% yield.

GLC, IR, NMR and mass spectral analysis yield the information that thereaction product contains the compounds having the structures:##STR198##

FIG. 44 is the GLC profile (fraction 3) for the reaction product ofExample XI containing the compounds having the structures: ##STR199##

FIG. 45 is the mass spectrum for the reaction product of Example XI,containing the compounds having the structures: ##STR200##

FIG. 46 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example XI containing the compounds havingthe structures: ##STR201##

FIG. 47 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XI containing the compoundshaving the structures: ##STR202##

EXAMPLE XII PREPARATION OF1,2,3,4,4A,5,8,8A-OCTAHYDRO-1,2,2,8A-TETRAMETHYL-1-NAPHTHOL Reaction##STR203##

Into a two liter reaction vessel equipped with thermometer, stirrer,addition funnel and reflux condenser are placed 620 ml (1.86 moles) ofmethyl magnesium chloride (3 M solution) dissolved in tetrahydrofuran.Into the addition funnel is placed a mixture of 250 ml tetrahydrofuranand 245 g (1.24 moles) of the ketone having the structure: ##STR204##prepared according to Example I.

Over a period of 3 hours the ketone/tetrahydrofuran solution is added tothe grignard reagent/tetrahydrofuran solution while maintaining thereaction temperature at 32° C. At the completion of the addition of theketone, the reaction mass is heated to a temperature in the range of27°-45° C. while refluxing the reaction mass.

At the end of the reaction (one hour) the reaction mass is added to oneliter of 20% acetic acid. The organic layer is washed with one liter of10% sodium chloride followed by 500 ml saturated sodium carbonatefollowed by 500 ml saturated sodium chloride. The aqueous layer isextracted with toluene and the toluene extract is combined with thewashed organic layer. The reaction product is then dried over anhydroussodium sulfate, stripped of solvent and distilled yielding the followingfractions: Fractions 2-11 are product, 86% yield.

    ______________________________________                                                 Vapor    Liquid            Weight of                                 Fraction Temp.    Temp.      mm/Hg  Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (g.)                                      ______________________________________                                        1        119/137  150/157    2.3    13.9                                      2        110      146        1.5    18.5                                      3        110      137        2.0    19.1                                      4        111      137        2.0    17.1                                      5        112      143        2.0    18.6                                      6        115      144        2.0    21.9                                      7        113      144        1.8    25.5                                      8        113      145        1.8    29.0                                      9        114      147        1.8    29.8                                      10       114      165        1.8    26.3                                      11       111      225        1.8    15.5                                      ______________________________________                                    

(Distillation carried out on 12 inch Goodlow column).

The reaction product has the structure: ##STR205## as confirmed by NMR,IR and mass spectral analysis.

FIG. 48 is the GLC profile for the crude reaction product after initialworkup of Example XII containing the compound having the structure:##STR206##

FIG. 49 is the mass spectrum for the reaction product of Example XIIcontaining the compound having the structure: ##STR207##

FIG. 50 is the NMR spectrum for fraction 6 of the distillation productof the reaction product of Example XII containing the compound havingthe structure: ##STR208##

FIG. 51 is the infrared spectrum for fraction 6 of the distillationproduct of the reaction product of Example XII containing the compoundhaving the structure: ##STR209##

EXAMPLE XIII PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO-1,2,2,6,(and7),8A-PENTAMETHYL-1-NAPHTHOL Reaction ##STR210##

Into a 250 ml reaction flask equipped with stirrer, thermometer, refluxcondenser and addition funnel is placed a mixture of 41 g (0.2 moles) ofthe mixture of ketones having the structures: ##STR211## preparedaccording to Example III, and 50 ml tetrahydrofuran.

Over a period of 15 minutes 100 ml of a 3 M solution of methylmagnesiumchloride (0.3 moles) is added to the reaction mass while maintaining thereaction mas at a temperature of less than 30° C. The reaction mass isthen stirred for a period of 5.5 hours at the end of which time thereaction is complete. The reaction mass is then added to a mixture of 50ml acetic acid and 100 ml water. The aqueous layer is separated, and theorganic layer is washed with saturated sodium chloride and saturatedsodium bicarbonate solution, followed by saturated sodium chloridesolution. The washed material is dried over anhydrous sodium sulfate andmicrodistilled yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        98/99   115/115    0.7    4.6                                        2        95      115        0.7    4.7                                        3        96      116        0.7    3.5                                        4        96      116        0.7    2.5                                        5        97      125        0.7    6.5                                        6        97      170        0.7    6.9                                        7        90      185        0.7    0.3                                        ______________________________________                                    

The yield is 50%. The reaction product containing compounds having thestructures: ##STR212## is confirmed to have these structures by means ofNMR, IR and mass spectral analysis.

FIG. 52 is the GLC profile for fraction 2 of the one plate distillationproduct of the reaction product of Example XIII containing the compoundshaving the structures: ##STR213##

FIG. 53 is the mass spectrum for the reaction product of Example XIIIcontaining the compounds having the structures: ##STR214##

FIG. 54 is the NMR spectrum for fraction 6 of the distillation productof the reaction product of Example XIII containing the compounds havingthe structures: ##STR215##

FIG. 55 is the infrared spectrum for fraction 6 of the distillationproduct of the reaction product of Example XIII containing the compoundshaving the structures: ##STR216##

EXAMPLE XIV PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO-1,2,2,8(and5),8A-PENTAMETHYL-1-NAPHTHOL Reaction ##STR217##

In a 1000 cc reaction flask equipped with stirrer, condenser,thermometer and dropping funnel is placed 687 cc (1.10 moles) of amethyllithium (1.6 M) in diethyl ether solution. The methyllithiumsolution is cooled to 10° C. While maintaining the reaction mass at10°-15° C., dropwise, 114.0 g (0.55 moles) of the mixture of ketoneshaving the structures: ##STR218## prepared according to Example VIA isadded. After addition, IR analysis and GLC analysis indicates that noneof the starting material remains.

The resulting organometallic compound is then hydrolyzed with 100 cc ofwater. The organic phase is separated from the aqueous phase and theorganic phase is dried over anhydrous magnesium sulfate, stripped ofsolvent and distilled on a 12 inch stone-packed column to yield thefollowing fracitons:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      mm/Hg  Fraction                                   No.      (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                       ______________________________________                                        1        65/110  120/130    1.0/0.8                                                                              4.0                                        2        120     135        0.8    10.0                                       3        120     140        0.8    24.0                                       4        120     145        0.8    42.0                                       ______________________________________                                    

The yield is 80.0 g, which represents 65% of theory.

NMR, IR and mass spectral analysis yield the information tht thereaction product contains two compounds having the structures:##STR219##

FIG. 56 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example XIV containing the compounds having thestructures: ##STR220##

FIG. 57 is the mass spectrum for the reaction product of Example XIVcontaining the compounds having the structures: ##STR221##

FIG. 58 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example XIV containing the compounds havingthe structures: ##STR222##

FIG. 59 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XIV containing the compoundshaving the structures: ##STR223##

EXAMPLE XV PREPARATION OF DECAHYDRO-1,2,2,8A-TETRAMETHYL-1-NAPHTHOLReaction ##STR224##

The alcohol (54 g) produced according to Example XII having thestructure: ##STR225## and 100 g of isopropyl alcohol and 0.05 g of a 10%palladium on carbon hydrogenation catalyst are placed in an autoclave.

Over a period of 2 days, while maintaining the hydrogenation pressure of37-50 psig at a temperature of 25° C., hydrogen is admixed with thereaction mass in a close system.

At the end of this time period the autoclave is opened and the contentsare filtered. The reaction product is stripped of solvent and dried overanhydrous magnesium sulfate and then distilled on a 12 inch stone-packedcolumn to yield a compound (52 g (96% yield), b.p. 120° C./0.8 mmHg), asconfirmed by NMR, IR and mass spectral analysis to have the structure:##STR226##

FIG. 60 is the GLC profile for the reaction product of Example XVcontaining the compound having the structure: ##STR227##

FIG. 61 is the mass spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR228##

FIG. 62 is the NMR spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR229##

FIG. 63 is the infrared spectrum for the reaction product of Example XVcontaining the compound having the structure: ##STR230##

EXAMPLE XVI PREPARATION OF DECAHYDRO-1,2,2,6,(and7),8A-PENTAMETHYL-1-NAPHTHOL Reaction ##STR231##

Into a 2000 cc reaction flask equipped with stirrer, condenser,thermometer and dropping funnel is placed 680 cc (2.04 moles) ofmethylmagnesium chloride (3 M) in a tetrahydrofuran solution. Dropwiseallowing a slow exotherm, 170 g (0.82 moles) of the mixture of ketoneshaving the structures: ##STR232## prepared according to Example IV, isadded to the reaction mass. After addition, the reaction mass isrefluxed for 16 hours while being monitored by GLC analysis in order toascertain completion.

The reaction mass is then hydrolyzed with 200 cc of saturated ammoniumchloride solution. The resulting hydrolyzed material is then extractedwith two 100 cc portions of toluene. The toluene extract is stripped oftoluene and distilled to yield the following fractions:

    ______________________________________                                                 Vapor    Liquid            Weight of                                 Fraction Temp.    Temp.      mm/Hg  Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (g.)                                      ______________________________________                                        1        120/120  127/130    0.9/0.9                                                                              10.0                                      2        120      130        0.8    38.0                                      3        125      135        0.8    37.0                                      4        125      140        0.8    32.0                                      5        125      180        0.8    46.0                                      ______________________________________                                    

The yield is 138.5 g by GLC analysis which is 75.6% of theory.

GLC, IR and mass spectral analysis yield the information that theresulting product is a mixture of compounds having the structures:##STR233##

FIG. 64 is the GLC profile of the reaction product (after 8 hoursreflux) for Example XVI containing the compounds having the structures:##STR234##

FIG. 65 is the mass spectrum for the reaction product of Example XVIcontaining the compounds having the structures: ##STR235##

FIG. 66 is the NMR spectrum of fraction 4 of the distillation product ofthe reaction product of Example XVI containing the compounds having thestructures: ##STR236##

FIG. 67 is the infrared spectrum for fraction 4 of the distillationproduct of the reaction product of Example XVI containing the compoundshaving the structures: ##STR237##

EXAMPLE XVII PATCHOULI PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                                            Parts by Weight                                           ______________________________________                                        Ingredient                                                                    Orange Oil            50                                                      Bergamot Oil          20                                                      Lime Oil              100                                                     Neroli Oil            5                                                       4-(4-Methyl-4-hydroxyamyl)                                                                          5                                                       Δ.sup.3 -cyclohexene carboxaldehyde                                     2,3,3A,4,5,7AHexahydro-6,7A,8,8-                                                                    100                                                     tetramethyl-1,5-methano-1Hinden-                                              1-ol (prepared according to the                                               process of Example I of U.S.                                                  Pat. No. 3,989,760 issued on                                                  November 2, 1976)                                                             1',2',3',4',5',6',7',8'-Octahydro-                                                                  50                                                      2',3'8',8'-tetramethyl-2'-aceto-                                              naphthone isomer mixture produced                                             according to the process of                                                   Example VII of Application for U.S.                                           Letters Pat. No. 434,948 filed                                                on January 21, 1974, now U.S.                                                 Pat. No. 3,911,018 issued on                                                  October 7, 1975                                                               Gamma Methyl Ionone   20                                                      1-acetyl-2,5,5-trimethylcyclo-                                                                      50                                                      heptane produced according to                                                 U.S. Pat. No. 3,869,411 issued                                                on March 4, 1975                                                              In the alternative one of                                                     the following ingredients:                                                    Methyl substituted oxobicyclo-4,4,0-decane                                                          100                                                     derivatives prepared according                                                to one of Examples I-XVI                                                       ##STR238##                                                                   Produced according to                                                         Example I                                                                      ##STR239##           100                                                     Produced according to                                                         Example II                                                                    Mixture of:           100                                                      ##STR240##                                                                   and                                                                            ##STR241##                                                                   Produced according to                                                         Example III                                                                   Mixture of:           100                                                      ##STR242##                                                                   and                                                                            ##STR243##                                                                   Produced according to                                                         Example IV                                                                    Mixture of:           100                                                      ##STR244##                                                                   and                                                                            ##STR245##                                                                   Produced according to                                                         Example V                                                                     Mixture of:           100                                                      ##STR246##                                                                   and                                                                            ##STR247##                                                                   Produced according to                                                         either of Examples VIA                                                        or VIB                                                                         ##STR248##           100                                                     Produced according to                                                         Example VIIA or VIIB                                                          Mixture of:           100                                                      ##STR249##                                                                   and                                                                            ##STR250##                                                                   Produced according to                                                         Example VIII                                                                  Mixture of:           100                                                      ##STR251##                                                                   and                                                                            ##STR252##                                                                   Produced according to                                                         Example IX                                                                     ##STR253##           100                                                     Produced according to                                                         Example X                                                                     Mixture of:           100                                                      ##STR254##                                                                   and                                                                            ##STR255##                                                                   Produced according to                                                         Example XI                                                                    Mixture of:           100                                                      ##STR256##                                                                   and                                                                            ##STR257##                                                                   Prepared by reacting                                                          CH.sub.3 Li with product of                                                   Example XI                                                                     ##STR258##           100                                                     Produced according                                                            to Example XII                                                                Mixture of:           100                                                      ##STR259##                                                                   and                                                                            ##STR260##                                                                   Produced according                                                            to Example XIII                                                               Mixture of:           100                                                      ##STR261##                                                                   and                                                                            ##STR262##                                                                   Produced according                                                            to Example XIV                                                                 ##STR263##           100                                                     Produced according to                                                         Example XV                                                                    Mixture of:           100                                                      ##STR264##                                                                   and                                                                            ##STR265##                                                                   Produced according                                                            to Example XVI                                                                ______________________________________                                    

The methyl substituted oxobicyclo-4,4,0-decane derivatives preparedaccording to one of Examples I-XVI, when added to this formulation inthe amount indicated; and also in amounts up to 30% by weight of thetotal mixture; or in amounts as little as 1.0% by weight of thismixture, imparts aroma characteristics to this patchouli composition, inaddition to the patchouli aroma as follows:

                  TABLE II                                                        ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR266##     Minty, camphoraceous, dry woody with floral citrus                            background.                                                   Produced according to                                                         Example I                                                                      ##STR267##     A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                    Produced according to                                                         Example II                                                                     ##STR268##     A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.            and                                                                            ##STR269##                                                                   Produced according to                                                         Example III                                                                    ##STR270##     A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                   and                                                                            ##STR271##                                                                   Produced according to                                                         Example IV                                                                     ##STR272##     A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                   and                                                                            ##STR273##                                                                   Produced according to                                                         Example V                                                                      ##STR274##     A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                     and                                                                            ##STR275##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR276##     A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                 Produced according to                                                         Examples VIIA or VIIB                                                          ##STR277##     An intense patchouli-like aroma with a woody back-                            ground                                                        and                                                                            ##STR278##                                                                   Produced according to                                                         Example VIII                                                                   ##STR279##     Sandalwood, patchouli-like aroma with incense-like                            undertones                                                    and                                                                            ##STR280##                                                                   Produced according to                                                         Example IX                                                                     ##STR281##     An intense patchouli-like aroma with a woody back-                            ground                                                        and                                                                            ##STR282##                                                                   Produced according to                                                         Example VIII                                                                   ##STR283##     Sandalwood, patchouli-like aroma with incense-like                            undertones                                                    and                                                                            ##STR284##                                                                   Produced according to                                                         Example IX                                                                     ##STR285##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with precious, woody undertones.                        Produced according to                                                         Example X                                                                      ##STR286##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with precious, woody undertones.                        and                                                                            ##STR287##                                                                   Produced according to                                                         Example XI                                                                     ##STR288##     A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli background                                        Produced according to                                                         Example XII                                                                    ##STR289##     A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                      and                                                                            ##STR290##                                                                   Produced according to                                                         Example XIII                                                                   ##STR291##     A patchouli aroma with minty topnotes                         and                                                                            ##STR292##                                                                   Produced according to                                                         Example XVI                                                                    ##STR293##     A patchouli aroma with minty topnotes                         Produced according to                                                         Example XV                                                                     ##STR294##     An earthy, camphoraceous aroma with patchouli background      and                                                                            ##STR295##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XVIII PREPARATION OF SOAP COMPOSITIONS PART A

A total of 100 g of soap chips produced from unperfumed sodium basetoilet soap made from tallow and coconut oil is mixed with 1 g of themethyl substituted oxobicyclo-4,4,0-decane derivatives preparedaccording to one of Examples I-XVI until a substantially homogeneouscomposition is obtained. The soap composition manifests an excellentpatchouli-like character having aroma nuances and undertones asindicated in Table III below.

PART B

A total of 100 g of soap chips produced from unperfumed sodium basetoilet soap made from tallow and coconut oil is admixed with 1 g of oneof the perfume compositions set forth in Example I-XVI until asubstantially homogeneous composition is obtained. The soap compositionsmanifest aromas as indicated in Table II, supra, with a characteristicpatchouli aroma.

                  TABLE III                                                       ______________________________________                                        Structure        Fragrance Profile                                            ______________________________________                                         ##STR296##      Minty, camphoraceous, dry woody with floral citrus                            backround.                                                   Produced according to                                                         Example I                                                                      ##STR297##      A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                   Produced according to                                                         Example II                                                                     ##STR298##      A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.           and                                                                            ##STR299##                                                                   Produced according to                                                         Example III                                                                    ##STR300##      A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                  and                                                                            ##STR301##                                                                   Produced according to                                                         Example IV                                                                     ##STR302##      A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                  and                                                                            ##STR303##                                                                   Produced according to                                                         Example V                                                                      ##STR304##      A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                    and                                                                            ##STR305##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR306##      A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                Produced according to                                                         Examples VIIA or VIIB                                                          ##STR307##      An intense patchouli-like aroma with a woody back-                            ground                                                       and                                                                            ##STR308##                                                                   Produced according to                                                         Example VIII                                                                   ##STR309##      Sandalwood, patchouli-like aroma with incense-like                            undertones                                                   and                                                                            ##STR310##                                                                   Produced according to                                                         Example IX                                                                     ##STR311##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     Produced according to                                                         Example X                                                                      ##STR312##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.-and                  ##STR313##                                                                   Produced according to                                                         Example XI                                                                     ##STR314##      A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli backround                                        Produced according to                                                         Example XII                                                                    ##STR315##      A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                     and                                                                            ##STR316##                                                                   Produced according to                                                         Example XIII                                                                   ##STR317##      A patchouli aroma with minty topnote                         and                                                                            ##STR318##                                                                   Produced according to                                                         Example XVI                                                                    ##STR319##      A patchouli aroma with minty topnotes                        Produced according to                                                         Example XV                                                                     ##STR320##      An earthy, camphoraceous aroma with patchouli background     and                                                                            ##STR321##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XIX PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder sold under the trademark "RINSO"are mixed with 0.15 g of a perfume composition containing one of themixtures prepared according to Example XVII until a substantiallyhomogeneous composition having patchouli fragrances with aroma nuancesas indicated in Table II is obtained.

EXAMPLE XX PREPARATION OF A COSMETIC BASE

A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25g of one of the perfume compositions of Examples XVII in a ball mill. Asecond cosmetic powder is similarly prepared except that the mixtureproduced in Example XVII is replaced with one of the products producedin one of Examples I-XVI, that is, one of the methyl substitutedoxobicyclo-4,4,0-decane derivatives of one of Examples I-XVI. Thecosmetic powder containing the materials of Example XVII have patchouliaromas with dominating undertones and nuances as indicated in Table II,supra, in Example XVII. The cosmetic powder produced using the materialsof one of Examples I-XVI have patchouli-like characters with aromanuances as indicated in the Table IV below:

                  TABLE IV                                                        ______________________________________                                        Structure        Fragrance Profile                                            ______________________________________                                         ##STR322##      Minty, camphoraceous, dry woody with floral citrus                            background.                                                  Produced according to                                                         Example I                                                                      ##STR323##      A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                   Produced according to                                                         Example II                                                                     ##STR324##      A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.           and                                                                            ##STR325##                                                                   Produced according to                                                         Example III                                                                    ##STR326##      A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                  and                                                                            ##STR327##                                                                   Produced according to                                                         Example IV                                                                     ##STR328##      A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                  and                                                                            ##STR329##                                                                   Produced according to                                                         Example V                                                                      ##STR330##      A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                    and                                                                            ##STR331##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR332##      A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                Produced according to                                                         Examples VIIA or VIIB                                                          ##STR333##      An intense patchouli-like aroma with a woody back-                            ground                                                       and                                                                            ##STR334##                                                                   Produced according to                                                         Example VIII                                                                   ##STR335##      Sandalwood, patchouli-like aroma with incense-like                            undertones                                                   and                                                                            ##STR336##                                                                   Produced according to                                                         Example IX                                                                     ##STR337##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     Produced according to                                                         Example X                                                                      ##STR338##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     and                                                                            ##STR339##                                                                   Produced according to                                                         Example XI                                                                     ##STR340##      A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli backround                                        Produced according to                                                         Example XII                                                                    ##STR341##      A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                     and                                                                            ##STR342##                                                                   Produced according to                                                         Example XIII                                                                   ##STR343##      A patchouli aroma with minty topnote                         and                                                                            ##STR344##                                                                   Produced according to                                                         Example XVI                                                                    ##STR345##      A patchouli aroma with minty topnotes                        Produced according to                                                         Example XV                                                                     ##STR346##      An earthy, camphoraceous aroma with patchouli backround      and                                                                            ##STR347##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XXI LIQUID DETERGENT CONTAINING METHYL SUBSTITUTEDOXOBICYCLO-4,4,0-DECANE DERIVATIVES PREPARED ACCORDING TO ONE OFEXAMPLES I-XVI

Concentrated liquid detergents with warm patchouli-like aromas havingundertones and aroma nuances as indicated in Table V, below, containing0.2%, 0.5% and 1.2% of one of the products produced in accordance withExample I-XVI (methyl substituted oxobicyclo-4,4,0-decane derivatives)are prepared by adding appropriate quantities of methyl substitutedoxobicyclo-4,4,0-decane derivatives as indicated in Table V, below, toliquid detergents known as P-87. The warm patchouli aroma of the liquiddetergents increases with increasing concentrations of methylsubstituted oxobicyclo-4,4,0-decane derivatives as indicated in Table V,below, with increasing aroma nuances as indicated in Table V, below:

                  TABLE V                                                         ______________________________________                                        Structure        Fragrance Profile                                            ______________________________________                                         ##STR348##      Minty, camphoraceous, dry woody with floral citrus                            background.                                                  Produced according to                                                         Example I                                                                      ##STR349##      A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                   Produced according to                                                         Example II                                                                     ##STR350##      A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.           and                                                                            ##STR351##                                                                   Produced according to                                                         Example III                                                                    ##STR352##      A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                  and                                                                            ##STR353##                                                                   Produced according to                                                         Example IV                                                                     ##STR354##      A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                  and                                                                            ##STR355##                                                                   Produced according to                                                         Example V                                                                      ##STR356##      A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                    and                                                                            ##STR357##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR358##      A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                Produced according to                                                         Examples VIIA or VIIB                                                          ##STR359##      An intense patchouli-like aroma with a woody back-                            ground                                                       and                                                                            ##STR360##                                                                   Produced according to                                                         Example VIII                                                                   ##STR361##      Sandalwood, patchouli-like aroma with incense-like                            undertones                                                   and                                                                            ##STR362##                                                                   Produced according to                                                         Example IX                                                                     ##STR363##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     Produced according to                                                         Example X                                                                      ##STR364##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     and                                                                            ##STR365##                                                                   Produced according to                                                         Example XI                                                                     ##STR366##      A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli backround                                        Produced according to                                                         Example XII                                                                    ##STR367##      A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                     and                                                                            ##STR368##                                                                   Produced according to                                                         Example XIII                                                                   ##STR369##      A patchouli aroma with minty topnotes                        and                                                                            ##STR370##                                                                   Produced according to                                                         Example XVI                                                                    ##STR371##      A patchouli aroma with minty topnotes                        Produced according to                                                         Example XV                                                                     ##STR372##      An earthy, camphoraceous aroma with patchouli backround      and                                                                            ##STR373##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XXII PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUME

The compositions of Example XXII are incorporated in colognes havingconcentrations of 2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 75%, 80%, 85% and90% aqueous ethanol and into handkerchief perfumes in concentrations of15%, 20%, 25%, 30%, 35% and 40% (in 80%, 85%, 90% and 95% aqueousethanol). The use of the compositions of Example XVII affords distinctand definitive patchouli aroma having nuances and undertones asindicated in Table II of Example XVII.

EXAMPLE XXIII COLOGNE AND HANDKERCHIEF PERFUME

The methyl substituted oxobicyclo-4,4,0-decane derivatives produced bythe processes of any of Examples I-XVI are incorporated into perfumeshaving concentrations of 2.0%, 2.5%, 3.0%, 4.5% and 5.0% in 75%, 80%,85% and 95% aqueous ethanol; into handkerchief perfumes atconcentrations of 8%, 10%, 12%, 15% and 25% (in 80%, 90% and 95% aqueousethanol). Each of the methyl substituted oxobicyclo-4,4,0-decanederivatives produced according to Examples I-XVI afford distinct anddefinitive warm patchouli-like aromas with various nuances andundertones as indicated in Table VI, below, to the handkerchief perfumesand to colognes.

                  TABLE VI                                                        ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR374##     Minty, camphoraceous, dry woody with floral citrus                            background.                                                   Produced according to                                                         Example I                                                                      ##STR375##     A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                    Produced according to                                                         Example II                                                                     ##STR376##     A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.            and                                                                            ##STR377##                                                                   Produced according to                                                         Example III                                                                    ##STR378##     A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                   and                                                                            ##STR379##                                                                   Produced according to                                                         Example IV                                                                     ##STR380##     A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                   and                                                                            ##STR381##                                                                   Produced according to                                                         Example V                                                                      ##STR382##     A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                     and                                                                            ##STR383##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR384##     A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                 Produced according to                                                         Examples VIIA or VIIB                                                          ##STR385##     An intense patchouli-like aroma with a woody background       and                                                                            ##STR386##                                                                   Produced according to                                                         Example VIII                                                                   ##STR387##     Sandalwood, patchouli-like aroma with incense-like                            undertones                                                    and                                                                            ##STR388##                                                                   Produced according to                                                         Example IX                                                                     ##STR389##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with precious,  woody undertones.                       Produced according to                                                         Example X                                                                      ##STR390##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with precious,  woody undertones.                       and                                                                            ##STR391##                                                                   Produced according to                                                         Example XI                                                                     ##STR392##     A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli background                                        Produced according to                                                         Example XII                                                                    ##STR393##     A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol undertones                                        and                                                                            ##STR394##                                                                   Produced according to                                                         Example XIII                                                                   ##STR395##     A patchouli aroma with minty topnotes                         and                                                                            ##STR396##                                                                   Produced according to                                                         Example XVI                                                                    ##STR397##     A patchouli aroma with minty topnotes                         Produced according to                                                         Example XV                                                                     ##STR398##     An earthy, camphoraceous aroma with patchouli background      and                                                                            ##STR399##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XXIV IMITATION OIL OF BLACK PEPPER FLAVOR FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Oil of Cubeb    40.0                                                          Alpha phellandrene                                                                            35.0                                                          Oil of Coriander                                                                              9.0                                                           Oil of Pimento Leaf                                                                           3.0                                                           Oil of Patchouli                                                                              0.2                                                           Alpha Pinene    1.5                                                           Beta Pinene     3.0                                                           Beta caryophyllene                                                                            4.0                                                           Dihydrocarveol  1.0                                                           Piperonal       0.8                                                           Piperine        1.0                                                           Piperidine      1.5                                                                           100.0       TOTAL                                             ______________________________________                                    

To half of this formulation 5% by weight of one of the materialsproduced according to either Example I or IV is added. Nothing is addedto the other half. The formulations are diluted in food grade alcohol atlevels of 50 ppm, 100 ppm, 150 ppm and 200 ppm in each of thecomparisons at each of the levels the formulations containing thematerials of Example I or IV have a stronger more natural-like blackpepper aroma and flavor characteristic with excellent and pleasantoriental flavor nuances and notes. Accordingly, the materials of ExampleI and IV are considered to advantageously augment the standard blackpepper oil (imitation) making it more natural-like.

To the foregoing material containing either of the substances of ExampleI or IV is added, in an equal quantity, 4-terpineol propionate. The4-terpineol propionate even enhances the flavor further insofar ascausing it to be more natural-like black pepper.

EXAMPLE XXV BASIC WALNUT FLAVOR FORMULATION

The following basic walnut formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Cyclotene              4                                                      Vanillin               1                                                      Butyl isovalerate      2                                                      Benzaldehyde           6                                                      2,3-Diethyl pyrazine (10% in food grade                                                              2                                                      ethyl alcohol)                                                                Ethyl-2-methyl valerate                                                                              2                                                      Gamma Butyrolactone    20                                                     Gamma Hexenyl lactone  10                                                     2,4-Decadienal (0.1% in food grade                                                                   0.5                                                    ethyl alcohol)                                                                2,4-Heptadienal (0.1% in food grade                                                                  0.5                                                    ethyl alcohol)                                                                Butylidene phthalide   2                                                      Propylene glycol USP   95                                                     ______________________________________                                    

The foregoing flavor formulation is divided into two parts. To the firstpart at the rate of 5% is added the methyl substitutedoxobicyclo-4,4,0-decane derivative prepared according to either ofExample XII or XIII. To the second part, nothing is added. Both flavorsare compared by a bench panel at the rate of 20 ppm in water. The flavorwith the addition of the product produced according to each of ExamplesXII and XIII have pleasant fresh walnut kernel taste with fresh walnutaromas not present in the basic walnut flavor formulation. Therefore,the flavors with the materials produced according to both Examples XIIand SIIII are preferred as being much more characteristic in the walnutflavor by the bench panel (unanimous preference). The flavor is alsoevaluated at 1 ppm and the same unaminous preference is obtained.

EXAMPLE XXVI BASIC ORAL HYGIENE FLAVOR FORMULATION

The following basic oral hygiene flavor formulation is prepared:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Peppermint oil  89.0                                                          Spearmint oil   2.0                                                           Clove oil       1.0                                                           Anethole        2.0                                                           Cardamon oil    0.1                                                           Wintergreen oil 5.0                                                           Cinnamic aldehye                                                                              0.9                                                           ______________________________________                                    

The basic oral hygiene flavor formulation is now divided into two parts.To the first part at the rate of 10% is added the methyl substitutedoxobicyclo-4,4,0-decane derivatives prepared according to each ofExamples II, X or XI. To the second part, nothing is added. The flavorwith the flavors with the addition of the materials produced accordingto either of Examples II, X or XI have fresher minty/eucalyptol aromaand flavor characteristics with woody notes. Therefore, the flavors withthe materials produced according to Examples II, X or XI are preferredby the bench panel.

EXAMPLE XXVII PREPARATION OF A SOAP COMPOSITION

One hundred grams of soap chips are produced according to Example V ofU.S. Pat. No. 4,058,487 issued on Nov. 15, 1977, as follows:

"The sodium salt of an equal mixture of C₁₀ -C₁₄ alkane sulfonate (95%active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrousisopropanol and 125 pounds of deionized water at 150° F. In this mixtureis dissolved 10 pounds of partially hydrogenated cocoanut oil fattyacids and 15 pounds of sodium mono-C₁₄ alkyl maleate, and the pH of thissolution is adjusted to 6.0 by the addition of a small amount of 50%aqueous solution of sodium hydroxide. The isopropanol is distilled off,and the remaining aqueous solution is drum dried. The resulting solidactives are then blended in a chip mixture with 10 pounds water, 0.2pounds titanium hydroxide and 0.7 pounds of one of the materialsproduced according to Examples I-XVI as enumerated in the Table below.The chips are then plodded into logs, cut to size and finally stampedinto bars having a pH of approximately 6.9."

Each of the perfumed soaps manifests aromas with strong patchouli notesas indicated in the Table VIII below:

                  TABLE VIII                                                      ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR400##     Minty, camphoraceous, dry woody with floral citrus                            background.                                                   Produced according to                                                         Example I                                                                      ##STR401##     A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                    Produced according to                                                         Example II                                                                     ##STR402##     A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.            and                                                                            ##STR403##                                                                   Produced according to                                                         Example III                                                                    ##STR404##     A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                   and                                                                            ##STR405##                                                                   Produced according to                                                         Example IV                                                                     ##STR406##     A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                   and                                                                            ##STR407##                                                                   Produced according to                                                         Example V                                                                      ##STR408##     A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                     and                                                                            ##STR409##                                                                   Produced according to                                                         Example VIA or VIB                                                             ##STR410##     A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                 Produced according to                                                         Examples VIIA or VIIB                                                          ##STR411##     An intense patchouli-like aroma with a woody back-                            ground                                                        and                                                                            ##STR412##                                                                   Produced according to                                                         Example VIII                                                                   ##STR413##     Sandalwood, patchouli-like aroma with incense-like                            undertones                                                    and                                                                            ##STR414##                                                                   Produced according to                                                         Example IX                                                                     ##STR415##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                      Produced according to                                                         Example X                                                                      ##STR416##     An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                      and                                                                            ##STR417##                                                                   Produced according to                                                         Example XI                                                                     ##STR418##     A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli background                                        Produced according to                                                         Example XII                                                                    ##STR419##     A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                      and                                                                            ##STR420##                                                                   Produced according to                                                         Example XIII                                                                   ##STR421##     A patchouli aroma with minty topnotes                         and                                                                            ##STR422##                                                                   Produced according to                                                         Example XVI                                                                    ##STR423##     A patchouli aroma with minty topnotes                         Produced according to                                                         Example XV                                                                     ##STR424##     An earthy, camphoraceous aroma with patchouli background      and                                                                            ##STR425##                                                                   Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XXVIII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 pounds of a detergent powder prepared according to U.S.Pat. No. 4,058,472 and containing 5% by weight of the sodium salts of amixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface activecomponent, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkylcatechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol and 40parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35% of sodiumtetrapyrophosphate, 30% of sodium silcate, 20% of sodium carbonate, 3%of sodium carboxymethyl cellulose and 7% of starch is mixed with 0.15grams of one of the methyl substituted oxobicyclo-4,4,0-decanederivatives produced according to one of Example I-XVI as set forth inTable IX, below, until a substantially homogeneous composition isobtained. Each of the compositions have excellent patchouli aromas withnuances and undertones as enumerated in the Table below:

                  TABLE IX                                                        ______________________________________                                        Structure        Fragrance Profile                                            ______________________________________                                         ##STR426##      Minty, camphoraceous, dry woody with floral citrus                            background.                                                  Produced according to                                                         Example I                                                                      ##STR427##      A sweet, fruity, minty, camphoraceous aroma with a woody                      patchouli undertone flavor characteristic.                   Produced according to                                                         Example II                                                                     ##STR428##      A green herbaceous aroma with a lavander top note and a                       basil/citrus undertone with bergamot-like nuances.           Produced according to                                                         Example III                                                                    ##STR429##      A peppery, dry woody aroma with a precious woody back-                        ground and vetiver-like and ambery nuances.                  Produced according to                                                         Example IV                                                                     ##STR430##      A citrus (lime) aroma with dry woody and patchouli                            undertones.                                                  Produced according to                                                         Example V                                                                      ##STR431##      A rich herbaceous lavander, thyme/rosemary aroma which                        becomes sweaty on dry out                                    Produced according to                                                         Example VIA or VIB                                                             ##STR432##      A patchouli, woody, camphoraceous aroma with a                                borneol-like undertone flavor                                Produced according to                                                         Examples VIIA or VIIB                                                          ##STR433##      An intense patchouli-like aroma with a woody back-                            ground                                                       Produced according to                                                         Example VIII                                                                   ##STR434##      Sandalwood, patchouli-like aroma with incense-like                            undertones                                                   Produced according to                                                         Example IX                                                                     ##STR435##      An earthy, camphoraceous, woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                     Produced according to                                                         Example X                                                                      ##STR436##      An earthy, camphoraceous,  woody, borneol-like, patchouli                      aroma with pre- cious, woody undertones.                    Produced according to                                                         Example XI                                                                     ##STR437##      A camphoraceous/borneol, earthy, rooty, woody aroma with                      a patchouli background                                       Produced according to                                                         Example XII                                                                    ##STR438##      A dry woody, rooty, patchouli aroma with campho- raceous                      and borneol under- tones                                     Produced according to                                                         Example XIII                                                                   ##STR439##      A patchouli aroma with minty topnotes                        Produced according to                                                         Example XVI                                                                    ##STR440##      A patchouli aroma with minty topnotes                        Produced according to                                                         Example XV                                                                     ##STR441##      An earthy, camphoraceous aroma with patchouli background     Produced according to                                                         Example XVI                                                                   ______________________________________                                    

EXAMPLE XXIX TOBACCO FILTER

Into a 20 mm cellulose acetate filter is added the mixture of ketoneshaving the structures: ##STR442## prepared according to Example VIA atthe rate of 1000 ppm (10 micro liters of a 10% solution of said ketonesare added to the filter). The filter is then attached to a full flavorcigarette on the market, e.g. (1) Marlboro®, (2) Winston® or (3)Viceroy®, as well as on a Kentucky 1A3 reference cigarette (produced bythe University of Kentucky) yielding the following results:

1. Both cigarettes containing the ketone mixture additive, when comparedto a cigarette having a filter without said ketone mixture additive,gives rise to a sweet, fruity, woody, cooling, floral and berry-likearoma on smoking with a pleasant cooling effect and rather noticeablereduced harshness.

2. Both cigarettes containing said ketone mixture additive, have alesser degree of "hotness" and give rise to a "fresh" taste on smoking.

EXAMPLE XXX TOBACCO FLAVOR FORMULATIONS

Cigarettes are produced using the following tobacco formulations:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           H.sub.2 O       5.3                                                           ______________________________________                                    

At the rate of 0.2%, the following tobacco flavor formulation is appliedto all of the cigarettes produced with the above tobacco formulation:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Ethyl butyrate   .05                                                          Ethyl valerate   .05                                                          Maltol           2.00                                                         Cocoa Extract    26.00                                                        Coffee Extract   10.00                                                        Ethyl Alcohol (95%)                                                                            20.00                                                        H.sub.2 O        41.90                                                        ______________________________________                                    

To portions of 50% of the cigarettes at levels of 10 and 20 ppm, methylsubstituted oxobicyclo-4,4,0-decane derivatives as indicated in Table Xbelow are added. These cigarettes are hereinafter called "experimental"cigarettes and the cigarettes without the methyl substitutedoxobicyclo-4,4,0-decane derivatives as set forth in Table X below, arehereinafter called "control" cigarettes. The "control" and"experimental" cigarettes are then evaluated by paired comparison andthe results are as follows:

a. In aroma, the "experimental" cigarettes are all found to be morearomatic with nuances as indicated in Table X below;

b. In smoke flavor, the "experimental" cigarettes are found to be morearomatic, more sweet with bitter, richer and less harsh nuances onsmoking in both the mainstream and the sidestream than the "control"cigarettes.

The "experimental" cigarettes containing 20 ppm of each of the compoundswhich are methyl substituted oxobicyclo-4,4,0-decane derivativesprepared according to the examples in the instant case and set forth inTable X below are found to be superior in flavor than those notcontaining such compounds:

                  TABLE X                                                         ______________________________________                                        Structure        Tobacco profile                                              ______________________________________                                         ##STR443##      A sweet, woody, citrusy aroma with cooling nuances prior                      to and on smoking in the main- stream and in the                              sidestream.                                                  Produced according to                                                         Example II                                                                     ##STR444##      A sweet, fruity, berry, cooling, woody, floral aroma                          both prior to and on smoking in the main- stream and in                       the sidestream.                                              Produced according to                                                         either of Examples VI(A)                                                      or VI(B)                                                                       ##STR445##      A sweet, woody, vetiver-like aroma and taste, both prior                      o and on smoking in the mainstream and the sidestream        Produced according                                                            to Example VII(A)                                                             or VII(B)                                                                      ##STR446##      A woody, patchouli-like, oriental-like, aroma both to                         and on smoking causing Virginia-like tobacco to attain a                      Turkish tobacco aroma and taste                              Produced according                                                            to Example VIII                                                                ##STR447##      A sweet, woody aroma and taste both prior to and on                           smoking                                                      Produced according                                                            to Example XI                                                                  ##STR448##      A sweet, woody, vertiver-like aroma and taste both prior                      o and smoking in the main- stream and the sidestream         Produced according                                                            to Example XII                                                                 ##STR449##      A woody, patchouli-like aroma and taste both prior to                         and on smoking yielding a cigar-type taste in the                             mainstream and the sidestream                                Produced according                                                            to Example XIV                                                                 ##STR450##      A woody, camphoraceous, and patchouli-like aroma and                          taste both prior to and on smoking with woody, oriental                       notes in the smoke causing it to be use- ful in the                           production of Turkish tobacco flavor, this material                           imparts a Turkish tobacco aroma and taste nuance to                           Virginia tobaccos in both the mainstream and the side-                        streams                                                      Prepared by reacting                                                          CH.sub.3 Li with product of                                                   Example XI                                                                     ##STR451##      A woody, patchouli-like aroma and taste both prior to                         and on smoking                                               Prepared according                                                            to Example XVI                                                                ______________________________________                                    

EXAMPLE XXXI A. POWDER FLAVOR COMPOSITION

20 Grams of the flavor composition of Example XXV is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.,and a wheel speed of 50,000 rpm.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Liquid Sweet Anise Flavor                                                                           20                                                      Composition of Example XXV                                                    Propylene glycol      9                                                       Cab-O-Sil® M-5                                                            (Brand of Silica produced by the                                              Cabot Corporation of 125 High Street,                                         Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft)                                                                             5.00                                                    ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid sweet anise flavor compositionsof Example XXV with vigorous stirring, thereby resulting in a viscousliquid. 71 Parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring, at25° C. for a period of 30 minutes resulting in a dry, free flowingsustained release flavor powder.

EXAMPLE XXXII

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleXXV is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coascervation is induced by adding, slowly and uniformly 40 parts of a20% aqueous solution of sodium sulphate. During coascervation thegelatin molecules are deposited uniformly about each oil droplet as anucleus.

Gelation is effected by pouring the heated coascervate mixture into1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65°F. The resulting jelled coascervate may be filtered and washed attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXXIII CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XXIX. 300 Parts of sucroseand 100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingwalnut flavor.

EXAMPLE XXXIV CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XXXII. 300 Parts of sucroseand 100 parts of corn syrup are then added. Mixing is effected in aribbon blender with jacketed side walls of the type manufactured by theBaker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingwalnut flavor.

EXAMPLE XXXV TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight                                                                            Ingredient                                                       ______________________________________                                        Group "A"                                                                     30.200       Glycerine                                                        15.325       Distilled water                                                   .100        Sodium Benzoate                                                   .125        Saccharin Sodium                                                  .400        Stannous Fluoride                                                Group "B"                                                                     12.500       Calcium Carbonate                                                37.200       Dicalsium Phosphate (Dihydrate)                                  Group "C"                                                                     2.000        Sodium N--Lauroyl Sarcosinate (foaming                                        agent                                                            Group "D"                                                                     1.200        Flavor Material of Example XXXI                                  100.00  (Total)                                                               ______________________________________                                         PROCEDURE:                                                                    1. The ingredients in Group "A" are stirred and heated in a steam jackete     kettle to 160° F.                                                      2. Stirring is continued for an additional three to five minutes to form      homogeneous gel                                                               3. The powders of Group "B" are added to the gel, while mixing, until a       homogeneous paste is formed                                                   4. With stirring, the flavor of "D" is added and lastly the sodium            nlauroyl sarcosinate                                                          5. The resultant slurry is then blended for one hour. The completed paste     is then transferred to a three roller mill and then homogenized, and          finally tubed                                                            

The resulting toothpaste when used in a normal tooth-brushing procedureyields a pleasant walnut flavor, of constant strong intensity throughoutsaid procedure (1-1.5 minutes).

EXAMPLE XXXVI CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example XXV isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich chewable vitamin tablet formulation is prepared as follows:

In a Hobart Mixer the following materials are blended to homogeneity:

    ______________________________________                                                             Gms/1000 tablets                                         ______________________________________                                        Vitamin C (ascorbic acid) as ascorbic                                         acid-sodium ascorbate mixture 1:1                                                                    70.00                                                  Vitamin B.sub.1 (thiamine mononitrate) as                                     Rocoat® thiamine mononitrate 331/3%                                       (Hoffman La Roche)     4.0                                                    Vitamin B.sub.2 (riboflavin) as Rocoat®                                   riboflavin 331/3%      5.0                                                    Vitamin B (pyridoxine hydrochloride) as                                       Rocoat® pyridoxine hydrochloride                                          331/3%                 4.0                                                    Niacinamide as Rocoat® niacinamide 331/3 %                                                       33.0                                                   Calcium pantothenate   11.5                                                   Vitamin B.sub.12 (cyanocobalamin) as Merck                                    0.1% in gelatin        3.5                                                    Vitamin E (dl-alpha tocopheryl acetate)                                       as dry Vitamin E acetate 331/3% Roche                                                                6.6                                                    d-Biotin               0.044                                                  Flavor of Example XXXI (as indicated above)                                   Certified lake color   5.0                                                    Sweetener - sodium saccharin                                                                         1.0                                                    Magnesium stearate lubricant                                                                         10.0                                                   Mannitol q.s. to make  500.0                                                  ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 G dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong walnut flavor for a period of 12 minutes.

EXAMPLE XXXVII CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at the rate of 30%:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Corn Syrup           60                                                       Licorice             10                                                       Glycerine            20                                                       Fig Juice            4.6                                                      Prune Juice          5                                                        Flavor Material of Example XXXI                                                                    0.4                                                      ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting walnut nuance in conjunction with the sweet tobacco note.

What is claimed is:
 1. A process for preparing a compound defined according to the structure: ##STR452## comprising the step of intimately admixing a compound having the structure: ##STR453## with an isopropyl magnesium halide in the presence of diethyl ether at a temperature of from 10° C. up to 30° C. in order to form an organometallic salt; then hydrolyzing the organometallic salt with an ammonium chloride solution; and then distilling the compound having the structure: ##STR454## from the reaction mass.
 2. The process of claim 1 wherein the isopropyl magnesium halide is isopropyl magnesium chloride.
 3. The process of claim 1 wherein the mole ratio of the compound having the structure: ##STR455## to the isopropyl magnesium halide is 1.5:1.
 4. The process of claim 1 wherein the reaction sequence carried out is: ##STR456##
 5. A process for forming at least one compound defined according to the structure: ##STR457## said reaction being carried out in the presence of a solvent selected from the group consisting of benzene, tetrahydrofuran and diethyl ether; wherein R₁, R₂, R₃ and R₄ each represents methyl or hydrogen; and wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond comprising the step of reacting a compound having the structure: ##STR458## with a compound having the structure:

    CH.sub.3 --M(R.sub.7).sub.n

wherein M represents MgX, Na, K, Li, Cd, Mg or Zn; wherein R₇ represents lower alkyl; wherein M is Cd, Mg or Zn when n=1, and M is MgX, Na, K or Li, when n=0, the mole ratio of organometallic compound having the structure:

    CH.sub.3 --M(R.sub.7).sub.n :

compound having the structure: ##STR459## is about 1:1, the reaction being carried out from about -5° C. up to about 40° C. in order to form a compound having the structure: ##STR460## hydrolyzing the compound having the structure: ##STR461## using a mineral acid selected from the group consisting of sulfuric acid, phosphoric acid and paratoluene sulphonic acid at a temperature of between 0° and 20° C.; and then isolating the compound having the structure: ##STR462## from the reaction mass.
 6. The process of claim 5 wherein the compound having the structure:

    CH.sub.3 --M(R.sub.7).sub.n

is methyl magnesium chloride. 